CN107999045A - A kind of aluminium oxide formed body and its preparation method and application and a kind of catalyst and preparation method and a kind of hydrotreating method - Google Patents
A kind of aluminium oxide formed body and its preparation method and application and a kind of catalyst and preparation method and a kind of hydrotreating method Download PDFInfo
- Publication number
- CN107999045A CN107999045A CN201610966177.6A CN201610966177A CN107999045A CN 107999045 A CN107999045 A CN 107999045A CN 201610966177 A CN201610966177 A CN 201610966177A CN 107999045 A CN107999045 A CN 107999045A
- Authority
- CN
- China
- Prior art keywords
- hydrated alumina
- wet gel
- formed body
- composition
- aluminium oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 562
- 238000000034 method Methods 0.000 title claims abstract description 232
- 239000003054 catalyst Substances 0.000 title claims abstract description 111
- 238000002360 preparation method Methods 0.000 title claims abstract description 61
- 239000011240 wet gel Substances 0.000 claims abstract description 138
- 239000000203 mixture Substances 0.000 claims abstract description 123
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 123
- 150000001875 compounds Chemical class 0.000 claims abstract description 85
- 238000000465 moulding Methods 0.000 claims abstract description 60
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 49
- 238000001035 drying Methods 0.000 claims abstract description 47
- 229910001593 boehmite Inorganic materials 0.000 claims abstract description 43
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims abstract description 43
- 239000012298 atmosphere Substances 0.000 claims abstract description 41
- 230000000694 effects Effects 0.000 claims abstract description 29
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000001301 oxygen Substances 0.000 claims abstract description 18
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 14
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 14
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims description 65
- 239000000499 gel Substances 0.000 claims description 64
- 239000007787 solid Substances 0.000 claims description 61
- 229910052751 metal Inorganic materials 0.000 claims description 58
- 238000000926 separation method Methods 0.000 claims description 58
- 230000008569 process Effects 0.000 claims description 45
- 239000000243 solution Substances 0.000 claims description 41
- 238000005406 washing Methods 0.000 claims description 31
- 229910052782 aluminium Inorganic materials 0.000 claims description 30
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 28
- 239000004411 aluminium Substances 0.000 claims description 25
- 238000002156 mixing Methods 0.000 claims description 25
- 239000007789 gas Substances 0.000 claims description 24
- 239000002184 metal Substances 0.000 claims description 24
- 239000003795 chemical substances by application Substances 0.000 claims description 22
- 238000004519 manufacturing process Methods 0.000 claims description 22
- 239000002002 slurry Substances 0.000 claims description 21
- 230000003647 oxidation Effects 0.000 claims description 20
- 238000007254 oxidation reaction Methods 0.000 claims description 20
- 230000032683 aging Effects 0.000 claims description 17
- 229910001679 gibbsite Inorganic materials 0.000 claims description 16
- 150000002739 metals Chemical class 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 229920000926 Galactomannan Polymers 0.000 claims description 15
- 238000001556 precipitation Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 13
- 150000004676 glycans Chemical class 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 11
- 229920001282 polysaccharide Polymers 0.000 claims description 11
- 239000005017 polysaccharide Substances 0.000 claims description 11
- 229920003086 cellulose ether Polymers 0.000 claims description 9
- 230000018044 dehydration Effects 0.000 claims description 9
- 238000006297 dehydration reaction Methods 0.000 claims description 9
- 206010013786 Dry skin Diseases 0.000 claims description 8
- 230000008859 change Effects 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 7
- 230000036571 hydration Effects 0.000 claims description 7
- 238000006703 hydration reaction Methods 0.000 claims description 7
- 229920000609 methyl cellulose Polymers 0.000 claims description 7
- 239000001923 methylcellulose Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000003463 adsorbent Substances 0.000 claims description 6
- 230000004087 circulation Effects 0.000 claims description 6
- 238000009826 distribution Methods 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- 238000011085 pressure filtration Methods 0.000 claims description 5
- 238000000605 extraction Methods 0.000 claims description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 4
- 229910052753 mercury Inorganic materials 0.000 claims description 4
- 150000002894 organic compounds Chemical class 0.000 claims description 4
- TWNIBLMWSKIRAT-RWOPYEJCSA-N (1r,2s,3s,4s,5r)-6,8-dioxabicyclo[3.2.1]octane-2,3,4-triol Chemical compound O1[C@@]2([H])OC[C@]1([H])[C@@H](O)[C@H](O)[C@@H]2O TWNIBLMWSKIRAT-RWOPYEJCSA-N 0.000 claims description 3
- 239000000969 carrier Substances 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims description 2
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims description 2
- 230000002431 foraging effect Effects 0.000 claims 1
- 239000000843 powder Substances 0.000 abstract description 40
- 239000003292 glue Substances 0.000 abstract description 13
- 239000002994 raw material Substances 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 239000000428 dust Substances 0.000 abstract description 7
- 239000007858 starting material Substances 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 238000012545 processing Methods 0.000 abstract description 4
- 239000003570 air Substances 0.000 description 71
- 238000001125 extrusion Methods 0.000 description 40
- 239000000463 material Substances 0.000 description 29
- 230000000052 comparative effect Effects 0.000 description 26
- 238000006243 chemical reaction Methods 0.000 description 22
- 239000003921 oil Substances 0.000 description 18
- 239000007790 solid phase Substances 0.000 description 18
- 238000002803 maceration Methods 0.000 description 16
- 238000007598 dipping method Methods 0.000 description 15
- 239000002253 acid Substances 0.000 description 14
- 238000007493 shaping process Methods 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 241000219782 Sesbania Species 0.000 description 12
- -1 aldehyde radical Chemical class 0.000 description 12
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 12
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 12
- 125000000217 alkyl group Chemical group 0.000 description 11
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 11
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 11
- 239000012065 filter cake Substances 0.000 description 10
- 238000001914 filtration Methods 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 9
- 229920001479 Hydroxyethyl methyl cellulose Polymers 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 229920003023 plastic Polymers 0.000 description 8
- 239000004033 plastic Substances 0.000 description 8
- 150000004645 aluminates Chemical class 0.000 description 7
- 239000002585 base Substances 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 229920002678 cellulose Polymers 0.000 description 7
- 239000001913 cellulose Substances 0.000 description 7
- 235000010980 cellulose Nutrition 0.000 description 7
- 239000013505 freshwater Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- 235000010981 methylcellulose Nutrition 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- 230000002829 reductive effect Effects 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 235000015424 sodium Nutrition 0.000 description 6
- 229910001388 sodium aluminate Inorganic materials 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- HIYNGBUQYVBFLA-UHFFFAOYSA-D cobalt(2+);dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Co+2].[Co+2].[Co+2].[Co+2].[Co+2].[O-]C([O-])=O.[O-]C([O-])=O HIYNGBUQYVBFLA-UHFFFAOYSA-D 0.000 description 5
- 229910000001 cobalt(II) carbonate Inorganic materials 0.000 description 5
- 238000007796 conventional method Methods 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 4
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 150000004682 monohydrates Chemical class 0.000 description 4
- 238000001935 peptisation Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- 159000000013 aluminium salts Chemical class 0.000 description 3
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 3
- 239000000908 ammonium hydroxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
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- 229910052750 molybdenum Inorganic materials 0.000 description 3
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- 229920005862 polyol Polymers 0.000 description 3
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- 239000011343 solid material Substances 0.000 description 3
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- 230000032258 transport Effects 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 229920002683 Glycosaminoglycan Polymers 0.000 description 2
- 229920000869 Homopolysaccharide Polymers 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical group [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
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- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
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- 239000001099 ammonium carbonate Substances 0.000 description 2
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- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
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- 239000011280 coal tar Substances 0.000 description 2
- 238000003869 coulometry Methods 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
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- 150000002484 inorganic compounds Chemical class 0.000 description 2
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- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
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- 238000003828 vacuum filtration Methods 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- OMDQUFIYNPYJFM-XKDAHURESA-N (2r,3r,4s,5r,6s)-2-(hydroxymethyl)-6-[[(2r,3s,4r,5s,6r)-4,5,6-trihydroxy-3-[(2s,3s,4s,5s,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxyoxan-2-yl]methoxy]oxane-3,4,5-triol Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@@H]1OC[C@@H]1[C@@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@@H](CO)O2)O)[C@H](O)[C@H](O)[C@H](O)O1 OMDQUFIYNPYJFM-XKDAHURESA-N 0.000 description 1
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 229920003139 Eudragit® L 100 Polymers 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229920001503 Glucan Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 230000019771 cognition Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 235000010944 ethyl methyl cellulose Nutrition 0.000 description 1
- 239000001761 ethyl methyl cellulose Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 229940097789 heavy mineral oil Drugs 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- KVOIJEARBNBHHP-UHFFFAOYSA-N potassium;oxido(oxo)alumane Chemical compound [K+].[O-][Al]=O KVOIJEARBNBHHP-UHFFFAOYSA-N 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000009790 rate-determining step (RDS) Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 235000014612 sandwich biscuits Nutrition 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/882—Molybdenum and cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
- C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
- C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
- C10G49/04—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used containing nickel, cobalt, chromium, molybdenum, or tungsten metals, or compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1022—Fischer-Tropsch products
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1033—Oil well production fluids
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of aluminium oxide formed body and its preparation method and application, the preparation method include the compound containing hydrated alumina and with least two proton acceptor sites andAfter the molding being worth for the hydrated alumina composition less than 1.8 is optionally dried, roasted in the presence of water vapor in oxygen-containing atmosphere.The invention also discloses the catalyst and preparation method and hydrotreating method with hydrogenation catalyst effect using the aluminium oxide formed body as carrier.The formed body with higher-strength is prepared by starting material of hydrated alumina wet gel in the present invention, eliminate for the step of drying hydrated alumina wet gel, simplifying overall craft flow, reduce overall operation energy consumption, the dust pollution due to triggering using boehmite dry glue powder as raw material is avoided, improves operating environment.The catalytic activity of raising is shown in hydrocarbon oil hydrogenation processing using the aluminium oxide formed body of the present invention as catalyst prepared by carrier.
Description
Technical field
The present invention relates to aluminium oxide field shaping technique, in particular it relates to a kind of aluminium oxide formed body and its system
Preparation Method and application, the invention further relates to a kind of using the aluminium oxide formed body as catalyst of carrier and preparation method thereof,
The invention further relates to a kind of hydrotreating method using the catalyst.
Background technology
In conventional methods where, aluminium oxide formed body, particularly gama-alumina formed body, because its with preferable pore structure,
Suitable ratio surface and higher heat-resistant stability, use frequently as the carrier of adsorbent or loaded catalyst.This oxidation
Aluminium usually by dried hydrated alumina, such as boehmite through being molded, it is dry after, high-temperature roasting obtains again.
Based on above-mentioned cognition, as shown in Figure 1, the hydrated alumina wet gel being prepared needs to be dried, intended
Boehmite dry glue powder, then using boehmite dry glue powder as starting point, adds extrusion aid and optional chemical peptizing agent
(inorganic acid and/or organic acid), through kneading aftershaping, molding is used as adsorbent or carrier after dry and optional roasting
Use.The main problem of this preparation method is that dust pollution is larger and high energy consumption.
In order to reduce dust pollution, improve operating environment, researcher recognizes that shaping raw material used should be changed, opens
Begin to attempt hydrated alumina wet gel or semiarid boehmite preparing aluminium oxide molding as raw material.
US4613585 discloses a kind of method for preparing alumina catalyst carrier, and this method comprises the following steps：
(a) aluminum sulfate solution and sodium aluminate solution are poured into the container equipped with deionized water at the same time, makes aluminum sulfate solution
Reacted with sodium aluminate solution, reaction condition pH6.0-8.5, temperature is 50-65 DEG C, thus prepares first containing amorphous
The aqueous slurry of aluminium hydroxide；
(b) sodium aluminate aqueous solution is added into the first aqueous slurry, the additive amount of the sodium aluminate aqueous solution is enough to neutralize institute
The first aqueous slurry is stated, the total amount of the sodium aluminate solution used in step (a) and step (b) is equivalent to the sulphur used in step (a)
Stoichiometric 0.95-1.05 of the amount of sour aluminium, thus prepares the second aqueous slurry, the Al of second aqueous slurry2O3Concentration is
7wt% or higher；
(c) amorphous hydroted alumina in the second aqueous slurry is filtered out, filter cake is obtained, is obtained first with dilute ammonia scrubbing
Filter cake, then washed with dilute nitric acid solution, finally washed again with dilute ammonium hydroxide, with remove sulfate anion and
Sodium cation impurity, while the pH of filter cake is adjusted in the range of 7.5-10.5；
(d) then, without the aging filter cake, on a filter press by the cake dewatering, and by its Al2O3Content improve to
28-35wt%, and in the range of pH is 7.5-10.5, mediate the filter cake in the mixer of a self-cleaning type, during stop
Between be 10s or longer, boehmite particle is grown up in a short time, thus obtain the dough containing these particles；
(e) dough for obtaining step (d) is extruded into extrudate, and then dry and roasting obtains extrudate.
From the point of view of method disclosed in US4613585, although hydrated alumina wet gel can be molded by this method, from
The preparation condition of amorphous hydroted alumina is all restricted to kneader device and kneading conditions, causes complex operation.Also, by
Carrier prepared by this method should be unable to have very high intensity, it is difficult to meet the requirement of commercial Application, its reason is by this
The content of Free water is high in extrudate prepared by method, and the extrudate obtained through dry and roasting is loose.Meanwhile using this method
Carrier is prepared, it is difficult to regulate and control to the pore structure of carrier, so as to it is difficult to meet the needs of a variety of use occasions.
CN103769118A discloses a kind of heavy-oil hydrogenation catalyst, including carrier and active ingredient, and carrier is aluminium oxide,
Active component is group VIII and/or the metal of group vib, and wherein group VIII metal is Co or Ni, and group vib metal is Mo or W, its
In, it is prepared by the boehmite shaping that the alumina support contents on dry basis is less than 50%.The contents on dry basis is 50%
The preparation process of following boehmite includes：(1) aluminum salt solution carries out neutralizing plastic reaction with precipitating reagent；(2) filter back
The solid product of harvest glue reaction；(3) solid product obtains contents on dry basis as less than 50% after drying.
CN103769118A uses contents on dry basis to prepare alumina support, contents on dry basis for less than 50% boehmite
Boehmite for less than 50% is then to be done the solid product separated from the mixture that plastic is reacted
Obtained from dry, in actual mechanical process, it is difficult the method carried out that this, which is one, and main cause is as follows：
(1) the boehmite viscosity not being completely dried is stronger, and transfer is difficult, easily causes secondary dust to pollute；
(2) dry all since surface, to the wet solid separated from the mixture that plastic is reacted
The drying that product carries out belongs to endless white drying, therefore there are sandwich biscuits phenomenon, the i.e. surface of part boehmite to be done
Dry (that is, Free water being substantially free of by dry surface), and internal wet state is still maintained (that is, for not by dry
Portion, the content of Free water keep dry substantially before level), since surface is dried, form hard particles, to it is this not
Peptizing agent and/or binding agent are added in the boehmite parched completely when through mediating aftershaping, is formed in drying process
Hard particles easily cause to block during extrusion, influence production efficiency；
(3) it is difficult to which the butt of stability contorting boehmite, butt is unstable to cause very big interference to shaping, make into
Type process is also highly unstable, causes the increase of substandard product amount, and production efficiency is low；
(4) CN103769118A in shaping using conventional moulding process, the boehmite used yet with it
Butt (for 35%-50%) far below conventional contents on dry basis (for 70% or so), i.e. water content height, in extrusion molding process
In will not substantially produce extrusion pressure, therefore the carrier that extrudate obtains after drying and roasting does not have mechanical strength substantially, only
Apply some external force, will dusting, do not possess the possibility of commercial Application, this is the greatest problem that the technology faces.
In conclusion how on the premise of guaranteeing to be met the alumina support of industrial application requirement, simplify oxygen
Change the preparation process flow of alumina supporter and reduce operation energy consumption, while mitigate the dirt of the dust in alumina support preparation process
Dye is still a technical problem urgently to be resolved hurrily.
The content of the invention
It is an object of the invention to simplify the preparation process flow of alumina support, mitigate carrying alumina preparation process mistake
Dust pollution in journey, while the carrier prepared can also meet industrial application requirement.
For US4613585 and CN103769118A when preparing alumina support problem encountered, hair of the invention
A person of good sense is off the beaten track, by the compound containing at least two proton acceptor sites in molecular structure and arises directly from synthetic reaction
The mixing of hydrated alumina wet gel, the mixture of formation can not only be molded, and be obtained through dry and optional roasting
To shaping physical efficiency have and meet the intensity of industrial requirements.The present invention is completed on this basis.
According to the first aspect of the invention, the present invention provides a kind of preparation method of aluminium oxide formed body, this method
Comprise the following steps：
(1) a kind of hydrated alumina composition is molded, obtains molding, the hydrated alumina composition contains
Hydrated alumina and the compound with least two proton acceptor sites,
The compositionIt is worth for less than 1.8, it is describedValue is measured using following methods：By composition described in 10g 120
It is 240 minutes dry DEG C in air atmosphere, the quality through dry composition is denoted as w1, calculated using Formulas IValue,
Alternatively, (2) molding that step (1) obtains is dried, and obtains through dry molding；
(3) in the presence of water vapor, the molding or step (2) step (1) obtained obtain through it is dry into
Type thing is roasted in oxygen-containing atmosphere.
According to the second aspect of the invention, the present invention provides a kind of method system as described in the first aspect of the present invention
Standby aluminium oxide formed body.
According to the third aspect of the present invention, the present invention provides a kind of production forming method of hydrated alumina, the party
Method comprises the following steps：
(1) a kind of alumina hydrate gel solution is provided, the alumina hydrate gel solution is washed, obtains the
Monohydrate alumina wet gel, the i values of the first hydrated alumina wet gel are not less than 60%, are preferably not lower than
61%, more preferably not above 82%, more preferably not higher than 80%, still more preferably for not higher than 78.5%,
The i values are measured using following methods：By 10g hydrated aluminas wet gel in 120 DEG C of dryings in air atmosphere
240 minutes, the quality through dry sample is denoted as w2, i values are calculated using Formula II,
(2) using the method described in the first aspect of the present invention by the first hydrated alumina wet gel and with least
It is molded after the compound mixing in two proton acceptor sites, optionally dry and roasting, so as to prepare aluminium oxide shaping
Body.
According to the fourth aspect of the present invention, the present invention provides a kind of production forming method of hydrated alumina, the party
Method comprises the following steps：
(1) a kind of alumina hydrate gel solution is provided, the alumina hydrate gel solution is washed, obtains the
Monohydrate alumina wet gel；
(2) the first hydrated alumina wet gel is handled using (2-1) or (2-2), obtains the second aqua oxidation
Aluminium wet gel,
The first hydrated alumina wet gel and aqueous mixtures are formed slurries by (2-1), and the slurries are carried out solid-liquid
Separation, obtains the second hydrated alumina wet gel；
The first hydrated alumina wet gel is carried out separation of solid and liquid by (2-2), obtains the second hydrated alumina wet gel,
In (2-1) and (2-2), the condition of the separation of solid and liquid make it that the i values of the second hydrated alumina wet gel are
Not less than 60%, 62%, more preferably not above 82% are preferably not lower than, more preferably not higher than 80%, more into one
Step is preferably not higher than 78.5%,
The i values are measured using following methods：By 10g hydrated aluminas wet gel in 120 DEG C of dryings in air atmosphere
240 minutes, the quality through dry sample is denoted as w2, i values are calculated using Formula II,
(3) using the method described in the first aspect of the present invention by the second hydrated alumina wet gel and with least
It is molded after the compound mixing in two proton acceptor sites, optionally dry and roasting, so as to prepare aluminium oxide shaping
Body.
According to the fifth aspect of the present invention, the present invention provides one kind by third aspect of the present invention or the 4th side
Aluminium oxide formed body prepared by the method described in face.
According to the sixth aspect of the invention, the present invention provides described in second aspect of the present invention or the 5th aspect
Application of the aluminium oxide formed body as carrier or adsorbent.
According to the seventh aspect of the present invention, the present invention provides a kind of catalyst with hydrogenation catalyst effect, this is urged
Agent contains the group VIII metallic element and vib metals element of carrier and load on the carrier, wherein, it is described
Carrier is the aluminium oxide formed body described in second aspect of the present invention or the 5th aspect.
According to the eighth aspect of the present invention, the present invention provides a kind of preparation of the catalyst with hydrogenation catalyst effect
Method, this method are included in supported on carriers group VIII metallic element and vib metals element, wherein, the carrier is
Aluminium oxide formed body described in second aspect of the present invention or the 5th aspect.
According to the ninth aspect of the present invention, the present invention provides a kind of hydrotreating method, this method is included in hydrogenation
Under treatment conditions, hydrocarbon ils is contacted with the catalyst with hydrogenation catalyst effect, wherein, the urging with hydrogenation catalyst effect
Agent is the catalyst described in the 7th aspect of the present invention or the catalysis prepared as the method described in the 8th aspect of the present invention
Agent.
With existing process (such as Fig. 1 that alumina support is prepared using boehmite dry glue powder as starting material
Shown technique) compare, the present invention is directly used as molding starting using the hydrated alumina wet gel that synthetic reaction is prepared
Raw material, has the advantage that：
(1) the step of being used to dry hydrated alumina wet gel in existing process is eliminated, and is preparing shaping raw material
When, boehmite dry glue powder is modulated into plastic material without additionally introducing water, simplifies overall craft flow, is reduced
Overall operation energy consumption；
(2) dust pollution due to triggering using boehmite dry glue powder as raw material is avoided, is greatly improved
Operating environment.
Existing process, such as US4613585 with directly preparing carrier using hydrated alumina wet gel as starting material
Compared with CN103769118A, technical process of the invention is more succinct, and operability is stronger, and can effectively improve final
The intensity of the formed body of preparation.The present invention can prepare the shaping with higher-strength by starting material of hydrated alumina wet gel
The reason for body, may is that：Compound with least two proton acceptor sites and the Free water in hydrated alumina wet gel
Interaction forms hydrogen bond, adsorbs the Free water in hydrated alumina wet gel, while have at least two proton acceptor sites
Compound also can with hydrated alumina molecular structure hydroxyl occur interaction of hydrogen bond, play the role of physics peptization,
So that hydrated alumina wet gel can not only be molded, and can be so that the formed body finally prepared has higher intensity.
Also, shown using aluminium oxide formed body according to the present invention as catalyst prepared by carrier in hydrocarbon oil hydrogenation processing
The catalytic activity improved is shown.
Brief description of the drawings
Attached drawing is for providing a further understanding of the present invention, and a part for constitution instruction, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.
Fig. 1 is moulding process flow process usually used in current commercial Application.
Fig. 2 is used for a kind of preferred embodiment for illustrating alumina producing forming method according to the present invention.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The endpoint of disclosed scope and any value are not limited to the accurate scope or value herein, these scopes or
Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively
It can be combined with each other between the endpoint value of a scope and single point value, and individually between point value and obtain one or more
New number range, these number ranges should be considered as specific open herein.
According to the first aspect of the invention, the present invention provides a kind of preparation method of aluminium oxide formed body, this method
Comprise the following steps：(1) a kind of hydrated alumina composition is molded, obtains molding；
Alternatively, (2) molding that step (1) obtains is dried, and obtains through dry molding；
(3) in the presence of water vapor, the molding or step (2) step (1) obtained obtain through it is dry into
Type thing is roasted in oxygen-containing atmosphere.
In step (1), the hydrated alumina composition contains hydrated alumina and has at least two proton acceptor positions
The compound of point.
The hydrated alumina can be more than one or both of gibbsite and a water aluminium oxide.It is described
Hydrated alumina preferably comprises a water aluminium oxide, more preferably a water aluminium oxide.The instantiation of the hydrated alumina can be with
Including but not limited to boehmite, gibbsite, unformed hydrated alumina and boehmite.In a kind of excellent of the present invention
In the embodiment of choosing, the hydrated alumina contains boehmite, more preferably boehmite.According to the preferable reality
The hydrated alumina composition of mode is applied particularly suitable for preparing the formed body as catalyst carrier.
The hydrated alumina is directed to hydrated alumina wet gel, is not originating from hydrated alumina dry glue powder.
In the present invention, term " hydrated alumina wet gel " refers to obtain by synthetic reaction and does not live through its i value being reduced to
The aqueous alumina hydrate gel of the dehydration of less than 60% (preferably less than 61%).In the present invention, i values are used with lower section
Method measures：10g hydrated aluminas wet gel is dried 240 minutes at 120 DEG C in air atmosphere, by the matter through dry sample
Amount is denoted as w2, i values are calculated using Formula II,
The synthetic reaction refers to the reaction for preparing gel aluminum hydroxide, can be aqua oxidation commonly used in the art
Alumina gel synthetic reaction, specific examples thereof include the precipitation method (including acid system and alkaline process), Hydrolyze method, kind point-score and fast dewatering
Method.The alumina hydrate gel of synthesis can be the alumina hydrate gel without going through aging, or live through aging
Alumina hydrate gel.The precipitation method, Hydrolyze method, kind point-score and rapid dehydration method concrete operation method and condition can be with
For conventional selection, will hereinafter illustrate.The hydrated alumina wet gel can be by the hydration that obtains synthetic reaction
After alumina gel alternatively carries out aging, carry out washing and separation of solid and liquid and collect solid phase and obtain.
It is different from the hydrated alumina from dry glue powder, it is directed to the aqua oxidation of alumina hydrate gel
Aluminium thing of hydrated alumina in storage process, which is met, to change.For example, it is small that 72 are placed under environment temperature and sealing condition
When, the thing of hydrated alumina, which is met, in the composition after placement changes.Depending on the environment temperature is with environment is placed, generally
It can be 5-50 DEG C, such as 20-40 DEG C.The sealing condition refers to the composition being placed in closure container, the closed appearance
Device can be closure container (such as tank, bucket or case), or the flexible coating (such as sealed bag) of sealing, the flexible bag
It can be paper and/or polymeric material to cover thing, be preferably polymeric material, such as plastics.
In an example, the hydrated alumina for being directed to alumina hydrate gel contains boehmite (as directly
It is boehmite to fetch and come from the hydrated alumina of alumina hydrate gel) when, by the composition in environment temperature and envelope
When placement 72 is small under the conditions of closing, the gibbsite content in the composition after placement is higher than three water in the composition before placing
Alumina content.In this example, on the basis of the total amount of the content of the gibbsite in the composition before placement, after placement
Composition in gibbsite content generally at least improve 0.5%, preferably at least improve 1%, preferably improve 1.1% to
2%, more preferably improve 1.1-1.5%.
Hydrated alumina composition also contains the compound with least two proton acceptor sites.Water according to the present invention
Alumina composition is closed, without being used as starting material using dry glue powder, you can for being molded (particularly extrusion molding), and obtain
There is formed body the reason for higher intensity may is that：The compound with least two proton acceptor sites and hydration
Interaction of hydrogen bond occurs for Free water in aluminium oxide wet gel, so as to adsorb Free water, while with hydrated alumina molecule knot
Hydroxyl in structure interacts, and plays the role of peptization.
In the compound with least two proton acceptor sites, proton acceptor site refers to point of the compound
The position of hydrogen bond can be formed in minor structure with water and hydroxyl.The instantiation in the proton acceptor site can include but unlimited
More than one or both of fluorine (F), oxygen (O) and nitrogen (N).The compound with least two proton acceptor sites
Instantiation can include but is not limited to contain selected from hydroxyl, carboxyl, amino, ehter bond, aldehyde radical, carbonyl, acid amides in molecular structure
The compound of group more than one or both of base and fluorine atom, is preferably hydroxyl and/or ehter bond.
The compound with least two proton acceptor sites can be organic compound, or inorganic chemical
Thing, can also be the combination of organic compound and inorganic compound.Using organising with least two proton acceptor sites
Compound, the organic compound can be removed by roasting process.Using the inorganic chemical with least two proton acceptor sites
Thing, the Partial Elements in the inorganic compound can be retained in the formed body finally prepared, it is possible thereby to inorganization by this
Compound introduces auxiliary element in formed body.
In a kind of preferred embodiment of the present invention, it is described there are at least two proton acceptor sites compound be
There is the polymer in multiple (such as more than three) proton acceptor sites in molecular structure.According to the preferred embodiment, can obtain
Physically better peptization is obtained, so that the intensity of the formed body finally prepared is further improved, particularly using extrusion work
When skill is molded, the intensity of the formed body finally prepared can be further improved.Preferably, the polymer is organic polymer
Thing.According to the preferred embodiment, the instantiation of the compound with least two proton acceptor sites can wrap
Include but be not limited to polyol, is more than one or both of polyethers and acrylic acid polymer.
The polyol can include but be not limited to polysaccharide, the etherate and polyalcohol of polysaccharide.
The polysaccharide can be homopolysaccharide, or heteroglycan, can also be the combination of homopolysaccharide and heteroglycan.It is described
Polysaccharide and its etherate specific examples thereof include but be not limited to glucan, galactan, mannosan, galactomannans, fibre
Dimension plain ether, starch, chitin, glycosaminoglycan and glycosaminoglycan.The cellulose ether refers to the part of hydroxyl in cellulosic molecule
On hydrogen atom substituted by alkyl after the ether system derivative that is formed, wherein, multiple alkyl can be identical, or no
Together.The alkyl is selected from the alkyl of substitution and unsubstituted alkyl.The unsubstituted alkyl be preferably alkyl (such as：C1-C5
Alkyl).In the present invention, C1-C5The instantiation of alkyl include C1-C5Straight chained alkyl and C3-C5Branched alkyl, can be with
For but be not limited to：Methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, n-pentyl, isopentyl and uncle penta
Base.The substituted alkyl for example can be substituted by hydroxyl, carboxyl, cyano group or aryl alkyl (such as：C1-C5By hydroxyl
Alkyl, the C of base substitution1-C5The alkyl substituted by carboxyl, the C that is substituted with aryl1-C5Alkyl), the aryl can be benzene
Base or naphthyl.The instantiation of the substituted alkyl can include but is not limited to：Cyano group, benzyl, phenethyl, hydroxyl first
Base, ethoxy, hydroxypropyl, hydroxyl butyl, carboxymethyl, carboxyethyl and carboxylic propyl group.The instantiation of the cellulose ether can include
But it is not limited to methylcellulose, hydroxyethylmethylcellulose, carboxymethyl cellulose, ethyl cellulose, benzylcellulose, ethoxy
Cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, cyanethyl cellulose, benzyl cyanethyl cellulose, carboxymethyl hydroxyl second
Base cellulose and benzyl cellulose.The etherate of the polysaccharide and polysaccharide can provide in a variety of manners.For example, galactomannan gathers
Sugar can be provided in the form of sesbania powder.
The polyalcohol specific examples thereof include but be not limited to polyvinyl alcohol, part acetalation polyvinyl alcohol (acetalizing degree
Can be less than 95%, be preferably less than 80%, more preferably less than 70%, more preferably less than 50%), polyether polyols
It is more than one or both of alcohol and polyester polyol.
The polyethers specific examples thereof include but be not limited to polyethylene oxide, polypropylene oxide, epoxy ethane-epoxy propane
Copolymer and PolyTHF.
The acrylic acid polymer refers to the polymer containing acrylic monomer unit, the acrylic monomer list
Member be specifically as follows but be not limited to acrylic monomer units and acrylate monomer units (be preferably C1-C5Alkyl acrylic
Monomeric unit, more preferably methacrylic acid monomer units).Specific examples thereof include polypropylene for the acrylic acid polymer
Acid, polymethylacrylic acid, copolymer of acrylic acid and methyl acrylate, acryl acid-methyl methacrylate copolymer, metering system
Acid-methyl acrylate copolymer and EUDRAGIT L100.
In the preferred embodiment, it is described there are at least two proton acceptor sites compound it is further preferably more
The etherate of sugar and/or polysaccharide, the more preferably etherate of polysaccharide and/or polysaccharide.
In a kind of embodiment being more highly preferred to of the present invention, the chemical combination with least two proton acceptor sites
Thing contains galactomannans and cellulose ether.The embodiment being more highly preferred to according to this, by the hydrated alumina composition
The formed body of formation has the intensity of higher.It is further preferred that the compound with least two proton acceptor sites
Preferably galactomannans and cellulose ether.
In the embodiment that this is more highly preferred to, with the total amount of the compound with least two proton acceptor sites
On the basis of, the content of the galactomannans can be 10-70 weight %, be preferably 15-68 weight %, more preferably 20-
65 weight %；The content of the cellulose ether can be 30-90 weight %, be preferably 32-85 weight %, more preferably 35-80
Weight %.
The hydrated alumina compositionIt is worth less than 1.8, to be preferably not higher than 1.7.The hydrated alumina combination
ThingValue is preferably more than 1.2, more preferably more than 1.3, more preferably more than 1.4.Specifically, the aqua oxidation
Aluminium compositionValue can be 1.2-1.8, be preferably 1.3-1.7, more preferably 1.4-1.7.
In the present invention,Value is measured using following methods：By composition described in 10g in 120 DEG C of dryings in air atmosphere
240 minutes, the quality through dry composition is denoted as w1, calculated using Formulas IValue,
Composition according to the present invention, the content of the compound with least two proton acceptor sites is can make institute
State compositionValue meets subject to above-mentioned requirements.Preferably, it is described to have at least relative to hydrated alumina described in 100 parts by weight
The content of the compound in two proton acceptor sites can be 1-25 weight %, be preferably 2-20 parts by weight, more preferably 3-15
Parts by weight, more preferably 3.5-10 parts by weight.
Composition according to the present invention, can contain peptizing agent, can not also contain peptizing agent.The peptizing agent can be
The usually used reagent with gelatification of aluminium oxide formed body preparing technical field, its instantiation can include but unlimited
In Aluminum sol, nitric acid, citric acid, oxalic acid, acetic acid, formic acid, malonic acid, hydrochloric acid and trichloroacetic acid.
Composition according to the present invention, the compound with least two proton acceptor sites, particularly described
It is described when compound with least two proton acceptor sites is containing polymer with least two proton acceptor sites
The compound with least two proton acceptor sites can play physics peptization, so as to reduce the use of peptizing agent
Amount, it might even be possible to without using peptizing agent.
In a kind of preferred embodiment of the present invention, relative to 100 parts by weight hydrated aluminas, the peptizing agent
Content is more preferably below 2 parts by weight below 5 parts by weight, to be preferably below 3 parts by weight.
In a kind of particularly preferred embodiment of the present invention, composition according to the present invention does not contain peptizing agent.
The hydrated alumina composition can be by by hydrated alumina and having at least two proton acceptor sites
Compound mixing and be made.As an example, prepare the hydrated alumina using method comprising the following steps and combine
Thing：A kind of each component in feedstock composition is mixed, obtains the hydrated alumina composition, that is, the mixture being mixed to get
For the hydrated alumina composition, the raw mixture contain hydrated alumina wet gel and with least two protons by
The compound of position point.
The hydrated alumina wet gel can use conventional method to synthesize, for example with the precipitation method (including acid system and alkali
Method), Hydrolyze method, kind one or both of point-score and rapid dehydration method more than method be made.Usually by hydrated alumina
After gel solution alternatively carries out aging, carry out washing and separation of solid and liquid obtained from.
The precipitation method include acid system and alkaline process.The acid system is that aluminium salt is carried out precipitation reaction with alkali compounds.Institute
It is that aluminate is carried out precipitation reaction with acid compound to state alkaline process.In the precipitation method, the mixture that precipitation reaction obtains is optional
After ground carries out aging (preferably carrying out aging), separation of solid and liquid is carried out, the solid phase isolated is washed, obtains the hydration
Aluminium oxide wet gel.
The aluminium salt and the species of the aluminate can be conventional selection.The instantiation of the aluminium salt can include but
It is not limited to more than one or both of aluminum sulfate, aluminium chloride and aluminum nitrate.The instantiation of the aluminate can include but
It is not limited to more than one or both of sodium metaaluminate, potassium metaaluminate and meta-aluminic acid magnesium.
The alkali compounds and the acid compound can be conventional selection.The alkali compounds can be common
It is various can make water in alkalescence compounds, ammonium hydroxide, hydroxide and basic salt can be selected from.The hydroxide can be normal
The water soluble hydroxide seen, such as alkali metal hydroxide.The basic salt can be that common decomposition in water make it that water is in
The salt of alkalescence, such as meta-aluminate, carbonate and bicarbonate.The instantiation of the alkali compounds can include but is not limited to
Ammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium metaaluminate, potassium metaaluminate, ammonium hydrogen carbonate, ammonium carbonate, sodium acid carbonate, sodium carbonate, carbonic acid
It is more than one or both of hydrogen potassium and potassium carbonate.The acid compound can be the common various changes that can make water in acidity
Compound, can be inorganic acid and/or organic acid.The instantiation of the acid compound can include but is not limited to sulfuric acid, salt
It is more than one or both of acid, nitric acid, carbonic acid, phosphoric acid, formic acid, acetic acid, citric acid and oxalic acid.The carbonic acid can be by leading
Enter carbon dioxide and generation in situ.
The precipitation reaction can carry out under normal conditions, this is not particularly limited in the present invention.Usually, the alkali
The dosage of the property compound either acid compound causes the pH of the aluminum salt solution or the aluminate solution to be 6-10,
Preferably 7-9.The precipitation reaction can carry out at a temperature of 30-90 DEG C, preferably 40-80 DEG C.
The method of hydrated alumina wet gel is prepared using Hydrolyze method to be included：Aluminum contained compound is hydrolyzed instead
Should, after the mixture that hydrolysis is obtained alternatively carries out aging (preferably carrying out aging), separation of solid and liquid is carried out, will be isolated
Solid phase washed, so as to obtain the hydrated alumina wet gel.
The aluminum contained compound can prepare the calorize that contains usually used in alumina hydrate gel technique for Hydrolyze method and close
Thing.The aluminum contained compound is preferably the organo-aluminum compound that hydrolysis can occur, more preferably aluminium alcoholates.It is described to contain calorize
The instantiation of compound can include but is not limited to aluminium isopropoxide, isobutanol aluminum, aluminium isopropoxide, three tert-butoxy aluminium and different
It is more than one or both of octanol aluminium.
The present invention is not particularly limited for the actual conditions of hydrolysis, can carry out under normal conditions.Usually,
The hydrolysis can be 3-11 in pH, be carried out under conditions of preferably 6-10.The hydrolysis can 30-90 DEG C,
It is preferred that carried out at a temperature of 40-80 DEG C.
In the precipitation method and Hydrolyze method, the condition of the aging is not particularly limited, and can carry out under normal conditions.One
As, the aging can carry out at a temperature of 35-98 DEG C, preferably 40-80 DEG C.The duration of the aging can be
When 0.2-6 is small.
The method of hydrated alumina wet gel is prepared using kind of point-score to be included：Added into supersaturated aluminate solution
Crystal seed, decomposes and produces aluminium hydroxide, and the mixture that decomposition is obtained carries out separation of solid and liquid, and the solid phase isolated is washed,
So as to obtain the hydrated alumina wet gel.The instantiation of the aluminate can include but is not limited to sodium metaaluminate, partially
It is more than one or both of potassium aluminate and meta-aluminic acid magnesium.
The method of hydrated alumina wet gel is prepared using rapid dehydration method to be included：By hydrated alumina in 600-
Roasted at a temperature of 950 DEG C, preferably 650-800 DEG C, product of roasting carries out hydro-thermal process, the mixing that hydro-thermal process is obtained
Thing carries out separation of solid and liquid, so as to obtain hydrated alumina wet gel.When the duration of the roasting can be 1-6 small, preferably
For 2-4 it is small when.The hydro-thermal process can carry out at a temperature of 120-200 DEG C, preferably 140-160 DEG C.The hydro-thermal process
Usually in closed container, carried out under self-generated pressure.
The precipitation method, Hydrolyze method, kind point-score and rapid dehydration method in, the separation of solid and liquid can use conventional method into
OK, it is specifically as follows the combination of filtering, centrifugation or both.
In the raw mixture, the i values of the hydrated alumina wet gel are not less than 60%, are preferably not lower than
61%.The i values of the hydrated alumina wet gel are preferably not higher than 82%, more preferably not above 80%, further preferably
For not higher than 78.5%.Specifically, the i values of the hydrated alumina wet gel can be 60-82%, be preferably 60-80%, more
Preferably 61-78.5%.
Can be by the way that separation of solid and liquid bar during separation of solid and liquid be carried out containing alumina hydrate gel solution to being prepared
Part is controlled, so as to obtain the hydrated alumina wet gel that i values meet above-mentioned requirements.In one embodiment of the present invention
In, separation of solid and liquid is more than once or twice, at least last time separation of solid and liquid is pressure filtration and/or vacuum filter.At this
In embodiment, by adjusting the pressure of application and/or the size of vacuum, carried out to obtaining hydrated alumina wet gel i values
Control.The instantiation for the device that the pressure filtration uses can include but be not limited to plate and frame type filter-press, belt type filter
The combination of machine or both.In order to control the i values of the hydrated alumina wet gel of acquisition, natural wind or with pressure can also be used
Wind purges isolated solid phase, so as to improve the efficiency of moisture abjection.The pressure of the wind with pressure can be conventional
Selection, generally can be 0.1-12MPa, be preferably 0.5-10MPa.
In the raw mixture, the hydrated alumina wet gel that separation of solid and liquid obtains is not lived through its i value drop generally
The dehydration of as low as less than 60% (preferably less than 61%).
In the raw mixture, the dosage of the compound with least two proton acceptor sites enables to most
The hydrated alumina composition prepared eventuallyValue meets previously described requirement.
The raw mixture can contain peptizing agent, can not also contain peptizing agent.Preferably, relative to 100 weight
Part hydrated alumina wet gel, the content of the peptizing agent are more preferably 2 below 5 parts by weight, to be preferably below 3 parts by weight
Below parts by weight, the hydrated alumina wet gel is in terms of hydrated alumina.It is highly preferred that the raw mixture does not contain glue
Solvent.
Conventional method can be used by hydrated alumina wet gel and the compound with least two proton acceptor sites
Mixing.Hydrated alumina wet gel and the compound with least two proton acceptor sites can be mixed under shear action
Close.In one embodiment, the mode of the mixing is stirring.Can be by hydrated alumina wet gel with having at least two
The two is uniformly mixed, so as to obtain institute by the compound in proton acceptor site in the container with agitating device by stirring
State hydrated alumina composition.The stirring can carry out in the container with agitating device, can also in beater into
OK.In another embodiment, the mode of the mixing is kneading.Can be by hydrated alumina wet gel with having at least two
The compound in a proton acceptor site is mediated in kneader, so as to obtain the hydrated alumina composition.It is described to pinch
The type of conjunction machine is not particularly limited.Stirring and hybrid combining can be used, by hydrated alumina wet gel with having extremely
The compound mixing in few two proton acceptor sites.At this time, preferably first it is stirred, then is mediated.
In mixed process, addition water can be supplemented, addition water can not also be supplemented, as long as can be so that the hydration oxygen prepared
Change aluminium compositionValue meets above-mentioned requirements.Usually, can be mixed from the angle for the uniformity for improving mixing
Supplement addition water during conjunction.Usually, the water and the weight of the compound with least two proton acceptor sites of addition are supplemented
It can be 5-15 to measure ratio：1, it is preferably 8-12：1.
In step (1), molding mode is not particularly limited, and can use various molding modes commonly used in the art, example
Such as：Extrusion, spraying, round as a ball, tabletting or combinations thereof.In a kind of preferred embodiment of the present invention, pass through extrusion
Mode is molded.
In step (1), molding according to specifically used requirement can have it is variously-shaped, such as：Spherical, honeycombed, bird
It is more than one or both of nest shape, piece shape or bar shaped (such as cloverleaf pattern, dish, cylinder and Raschig ring).
The molding that step (1) obtains, can be sent into step (2) and be dried by preparation in accordance with the present invention
Afterwards, it is sent into step (3)；The molding that can also obtain step (1), which is sent directly into step (3), to be roasted.
In step (2), the temperature that the molding is dried can be the conventional selection of this area.Usually, institute
Stating dry temperature can be more than 60 DEG C and be not higher than 350 DEG C, preferably 80-300 DEG C, be more preferably 110-260 DEG C.It is described
The dry time can make appropriate choice according to dry temperature.Usually, the duration of the drying can be 1-
48 it is small when, be preferably 2-24 it is small when, more preferably 2-12 it is small when, more preferably 2-4 it is small when.The drying can be oxygen-containing
Carry out in atmosphere (such as air atmosphere), can also in inert atmosphere (atmosphere that such as nitrogen and/or zero group gas are formed) into
OK, carried out preferably in oxygen-containing atmosphere.The drying can carry out under normal pressure (that is, 1 standard atmospheric pressure), can also depressurize
Under conditions of carry out.
In step (3), the temperature of the roasting can be 400-1200 DEG C, be preferably 450-1100 DEG C, more preferably
500-1000℃.When the duration of the roasting can be 1-20 small, when being preferably 1.5-15 small, more preferably 2-12 is small
When, when more preferably 2-4 is small.
In step (3), when being roasted, the heating rate for raising the temperature to calcination temperature can be conventional selection.
Usually, will accommodate molding container in temperature be increased to calcination temperature heating rate can be 10-400 DEG C/h,
Preferably 30-350 DEG C/h, more preferably 60-300 DEG C/h, more preferably 100-200 DEG C/h.It will can hold
The temperature received in the container of molding is increased to calcination temperature from environment temperature, can also be by the temperature in the container for accommodating molding
Degree is increased to calcination temperature from drying temperature, is not particularly limited.
In step (3), the roasting carries out under water vapour in oxygen-containing atmosphere, and the alumina support thus prepared has
The pore volume of higher and the specific surface area of bigger, so as to effectively lift the performance of aluminium oxide formed body.
By in roasting process, the air-flow of moisture vapor can be passed through into the container for accommodating molding, so as to fulfill
Roasted in the presence of water vapor.The dosage (intake) of water vapour can make choice according to the amount of molding.Generally
Ground, the dosage of water vapour can be 0.01-0.8L/ (ming moldings), be preferably 0.02-0.6L/ (ming moldings),
0.03-0.5L/ (ming moldings), the molding is in terms of hydrated alumina.
The air-flow of the moisture vapor can contain carrier gas, can not also contain carrier gas.The carrier gas can be air, zero group
Combinations more than one or both of elemental gas (such as argon gas and/or helium) and nitrogen.
The water vapour can be the water vapour in various sources.In a preferred embodiment, in step (3) extremely
The water vapour that small part water vapour produces for the molding that step (1) obtains in drying or roasting process.
Specifically, when the molding that step (1) obtains is sent into step (2) and is dried, drying process can be collected
The water vapour of middle generation, and the water vapour at least partly produced in the drying process is sent into step (3).At this time, according to dry
The water vapour amount that dry process produces, can mend fresh water vapour, can not also supplement fresh water vapour.Term " fresh water vapour "
The water vapour produced in dry and roasting process is different from, is referred in the method by the present invention outside dry and roasting process
The water vapour that water vapour generating process produces.The whole water vapours that drying process can be produced are sent into step (3).Can also
The part water vapour produced by during is sent into step (3).Preferably, the 10-90 bodies in gas drying process produced
Product %, preferably 30-88 volumes %, more preferably 60-90 volumes % is sent into step (3).
When the molding that step (1) obtains is sent directly into and is roasted in step (3), roasting process (bag can be collected
Include the temperature-rise period for raising the temperature to calcination temperature) in the water vapour that produces, and will be at least partially in being produced in roasting process
Water vapour circulation be sent into step (3).In actual mechanical process, molding can will be accommodated during heating and roasting
Container in gas draw, and using at least part gas of extraction as in the circulating air circulation feeding container.It can incite somebody to action
The gas all drawn is sent into the container as circulating air circulation, can also be followed the gas that part is drawn as circulating air
Ring is sent into the container.Preferably, it is sent into the gas that part is drawn as circulating air circulation in the container, at this time preferably
Fresh water vapour is supplemented into the container.It is highly preferred that by 10-90 volumes %, the preferably 30-88 bodies in the gas of extraction
The % circulations of product %, more preferably 60-90 volumes are sent into the container.
Roasting carries out in oxygen-containing atmosphere described in step (3), so that hydrated alumina is transformed into aluminium oxide.In order to
So that alumina hydrate gel becomes aluminium oxide with the conversion of higher, preferably in roasting process, to receiving molding
Container in be sent into oxygen-containing gas.The oxygen-containing atmosphere can be the mixing of oxygen, air or oxygen and non-active gas
Gas, the instantiations of the non-active gas can include but is not limited to nitrogen and/or group 0 element gas (such as argon gas and/or
Helium).Oxygen-containing gas can be sent into the container for accommodating molding together with water vapour.
The aluminium oxide formed body prepared by the method for the present invention has abundant pore structure, and pore-size distribution is adjustable, fits
In the carrier as adsorbent or catalyst.
Thus, according to the second aspect of the invention, the present invention provides oxidation prepared by a kind of method by the present invention
Aluminium formed body.
The pore-size distribution of aluminium oxide formed body according to the present invention is in Unimodal Distribution.Wherein, measured by mercury injection method, most probable
Aperture is 4-60nm, is preferably 5-40nm, more preferably 6-20nm, more preferably 7-15nm.
Aluminium oxide formed body according to the present invention, has higher intensity.Usually, aluminium oxide shaping according to the present invention
The radial direction crushing strength of body is more than 10N/mm, is preferably 15-30N/mm such as 10-40N/mm.In the present invention, using RIPP
The radial direction crushing strength of method measure formed body specified in 25-90.
According to the third aspect of the present invention, as shown in Fig. 2, the production the present invention provides a kind of hydrated alumina is molded
Method, this method comprise the following steps：
(1) a kind of alumina hydrate gel solution is provided, the alumina hydrate gel solution is washed, obtains the
Monohydrate alumina wet gel；
Alternatively, (2) are handled the first hydrated alumina wet gel using (2-1) or (2-2), obtain the second water
Aluminium oxide wet gel is closed,
The first hydrated alumina wet gel and aqueous mixtures are formed slurries by (2-1), and the slurries are carried out solid-liquid
Separation, obtains the second hydrated alumina wet gel；
The first hydrated alumina wet gel is carried out separation of solid and liquid by (2-2), obtains the second hydrated alumina wet gel,
In (2-1) and (2-2), the condition of the separation of solid and liquid make it that the i values of the second hydrated alumina wet gel are
Not less than 60%, 61%, more preferably not above 82% are preferably not lower than, more preferably not higher than 80%, more into one
Step is preferably not higher than 78.5%,
The i values are measured using following methods：By 10g hydrated aluminas wet gel in 120 DEG C of dryings in air atmosphere
240 minutes, the quality through dry sample is denoted as w2, i values are calculated using Formula II,
(3) using the method described in the first aspect of the present invention by the first hydrated alumina wet gel or described the
Two hydrated alumina wet gels are molded after being mixed with the compound with least two proton acceptor sites, are optionally done
Dry and roasting, so as to prepare aluminium oxide formed body.
In step (1), the alumina hydrate gel solution refers to alumina hydrate gel synthetic reaction obtains, process
Or the solution containing alumina hydrate gel without aging.The alumina hydrate gel solution can be prepared in situ
Alumina hydrate gel solution that is obtaining or coming from the transport of other production scenes.Preferably, the aqua oxidation
Alumina gel solution is the hydrated alumina wet gel solution being prepared in situ.The synthetic method and condition of alumina hydrate gel
Have been carried out being described in detail above, details are not described herein again.
Since the alumina hydrate gel solution that synthetic reaction obtains has an acid-base property, to hydrated alumina in step (1)
Wet gel is washed, and to remove acidic materials and alkaline matter therein, avoids the presence pair of acidic materials and alkaline matter
The adverse effect that alumina hydrate gel produces, while improve the solid content of alumina hydrate gel solution.Described in step (1)
Washing can carry out under normal conditions, as long as can be by the acidic materials and the amount of alkaline matter in alumina hydrate gel solution
Satisfaction is reduced to usually require that.
In step (1), separation of solid and liquid is directed in washing process, washings are extruded, obtain the first aqua oxidation
Aluminium wet gel.The i values of the first hydrated alumina wet gel can be meet described in the first aspect of the present invention with
The i values of the hydrated alumina wet gel of the compound mixing at least two proton acceptor sites, or higher than of the invention the
The i values of the hydrated alumina wet gel mixed with the compound with least two proton acceptor sites described in one side.
In one embodiment, the i values content of the first hydrated alumina wet gel meets first side of the invention
The i values of the hydrated alumina wet gel mixed with the compound with least two proton acceptor sites described in face, i.e., it is described
The i values of first hydrated alumina wet gel are not less than 60%, are preferably not lower than 61%.In this embodiment, described
The i values of monohydrate alumina wet gel are preferably not higher than 82%, more preferably not above 80%, are more preferably not higher than
78.5%.Specifically, the i values of the hydrated alumina wet gel can be 60-82%, be preferably 60-80%, more preferably
61-78.5%.
According to the embodiment, the first hydrated alumina wet gel can be sent directly into step (3), and with extremely
The compound mixing in few two proton acceptor sites.This is especially suitable for meeting occasion claimed below：(A) in wash mill
Solid-liquid separating equipment has preferable separating capacity, it is sufficient to which the i values control of the first hydrated alumina wet gel is above-mentioned to meet
Scope；(B) wash mill compact can be set with mixing arrangement so that the discharging of wash mill can be directly entered mixing dress
Put.
According to the embodiment, the first hydrated alumina wet gel can also be sent into step (2), using (2-1)
Handled.This is especially suitable for meeting occasion claimed below：(A) solid-liquid separating equipment in wash mill has preferable
Separating capacity, it is sufficient to control the i values of the first hydrated alumina wet gel to meet above range；(B) wash mill is with mixing
Device compact can not be set, so that the discharging of wash mill can not be directly entered mixing arrangement.
In another embodiment, the i values of the first hydrated alumina wet gel are higher than 82%, can not meet the present invention
The requirement mixed with the compound with least two proton acceptor sites described in the first aspect.According to the embodiment,
The first hydrated alumina wet gel is sent into step (2), is handled using (2-1) or (2-2).
The embodiment especially suitable for the solid-liquid separating equipment in wash mill separating capacity or operating condition not
Be enough by the control of the i values of the first hydrated alumina wet gel for meet the occasion of the requirement described in the first aspect of the present invention, with
And wash mill and mixing arrangement can not compact setting occasion.
In step (2), the first hydrated alumina wet gel is handled using (2-1) or (2-2), obtains second
Hydrated alumina wet gel.
In (2-1), the first hydrated alumina wet gel is mixed with water, slurries is formed, can so improve aqua oxidation
Aluminium wet gel transports performance.In (2-1), the additive amount of water, which is subject to the slurries to be formed, can meet to transport requirement, Ke Yigen
Made choice according to specific conveying equipment.
The i values for the second hydrated alumina wet gel that step (2) obtains meet described in the first aspect of the present invention
The i values of the hydrated alumina wet gel mixed with the compound with least two proton acceptor sites, i.e., described aqua oxidation
The i values of aluminium wet gel are not less than 60%, are preferably not lower than 61%.The i values of the second hydrated alumina wet gel are preferred
Not higher than 82%, 80% to be more preferably not above, more preferably not higher than 78.5%.
The second water that i values meet above-mentioned requirements can be obtained by the condition of separation of solid and liquid described in rate-determining steps (2)
Close aluminium oxide wet gel.The method of the i values of hydrated alumina wet gel is adjusted by selecting solid-liquid separating method and its condition
Have been carried out being described in detail above, be no longer described in detail herein.
In step (3), using the method described in the first aspect of the present invention by the first hydrated alumina wet gel or
Two hydrated alumina wet gels are molded after being mixed with the compound with least two proton acceptor sites, are optionally done
Dry and roasting, so as to prepare aluminium oxide formed body.It is sent into the first hydrated alumina wet gel and the second hydration of step (3)
The i values of aluminium oxide wet gel meet described in the first aspect of the present invention with the compound with least two proton acceptor sites
The i values of the hydrated alumina wet gel of mixing.
The method described in the 3rd aspect can be implemented in a kind of alumina producing formation system according to the present invention, the production
Formation system includes alumina hydrate gel production unit, separation of solid and liquid and washing unit, mixed cell, forming unit, optional
Drying unit and roasting unit.
The alumina hydrate gel solution output port of the alumina hydrate gel production unit and the separation of solid and liquid
And the washing material input port to be separated of washing unit is connected, the solid-phase material output of the separation of solid and liquid and washing unit
Port is connected with the solid-phase material input port of the mixed cell, the mixed material output port of mixed cell with it is described into
The raw material input port of type unit is connected, the material to be dried input port of the drying unit and the forming unit into
Type thing output port is connected, and the dried material of the material input port to be roasted and the drying unit of the roasting unit is defeated
The molding output port of exit port or the forming unit is connected,
The roasting unit includes being used for the container and water vapour conveying subelement for accommodating material to be roasted, the water
Steam conveying subelement is used to input water vapour into the container in roasting process.
The alumina hydrate gel production unit is used to generate alumina hydrate gel solution by synthetic reaction.Synthesis
The method of alumina hydrate gel can be conventional method, the precipitation method as previously described, Hydrolyze method, kind point-score and quick de-
Water law, is not described in detail herein.
The alumina hydrate gel production unit can use conventional reactor to carry out synthetic reaction, so as to obtain water
Alumina gel solution is closed, this is not particularly limited in the present invention.
The separation of solid and liquid and washing unit are used for the aqua oxidation for exporting the alumina hydrate gel production unit
Alumina gel aqueous solution carries out separation of solid and liquid and washing, obtains hydrated alumina wet gel, the hydrated alumina wet gelValue
Meet the requirement that can be mixed with the compound with least two proton acceptor sites described in the first aspect of the present invention.
The separation of solid and liquid and washing unit can use common various methods to carry out separation of solid and liquid and washing, so that
ArriveValue meets to mix desired alumina hydrate gel with the compound with least two proton acceptor sites.The solid-liquid
Separation and washing unit can use conventional equipment for separating liquid from solid, such as：The group of filtration apparatus, centrifugal device or both
Close.When separation of solid and liquid and washing unit include filtration apparatus, the filtration apparatus can be gravity filter device, pressure filtration
One or more kinds of combinations in device and vacuum apparatus.Preferably, the filtration apparatus includes at least pressurization
Filtration apparatus.The instantiation of the pressure filter can include but be not limited to plate and frame type filter-press, band filter
Or both combination.In order to control the hydrated alumina wet gel of acquisitionValue, the separation of solid and liquid and washing unit may be used also
Including blow device, to be purged using natural wind or wind with pressure to isolated solid phase, so as to improve moisture abjection
Efficiency.The pressure of the wind with pressure can be conventional selection, generally can be 0.1-12MPa, be preferably 0.5-10MPa.
The separation of solid and liquid and washing unit can include one or more separation of solid and liquid subelement, preferably at least one
A separation of solid and liquid subelement and last separation of solid and liquid subelement are pressure filter and/or vacuum apparatus, so that
Obtain the solid-phase material (that is, hydrated alumina wet gel) that separation of solid and liquid and washing unit obtainValue can meet the present invention first
The requirement mixed with the compound with least two proton acceptor sites described in a aspect.By adjusting application pressure or
The size of person's vacuum, can be to the hydrated alumina wet gel finally obtainedValue is adjusted.The separation of solid and liquid and wash
When washing unit includes two or more separation of solid and liquid subelement, except last separation of solid and liquid subelement preferably use using pressure as
Outside the solid-liquid separation method of motive force, remaining separation of solid and liquid separation subelement can use pressure filter and/or vacuum
Filtration apparatus, can not also use pressure filter and vacuum apparatus, it is preferred to use pressure filter and/or vacuum
Filtration apparatus.
The separation of solid and liquid and washing unit can use conventional wash mill to wash the solid phase isolated.Example
Such as, washings can be sprayed to using spray equipment by the solid phase surface isolated.In order to improve washing effect and washing
Efficiency, can apply solid phase shearing and/or vibration, by shower water and solid phase during the spray or after the completion of spray
It is uniformly mixed, the shearing is for example stirred.
On the basis of the trend of alumina hydrate gel material flow, separation of solid and liquid and washing unit are arranged on hydrated alumina
Between gel production unit and mixed cell, the gel solution for alumina hydrate gel production unit to be exported is divided
From obtainingValue meets the hydrated alumina wet gel that mixing requires, and raw material is provided for mixed cell.
On the premise of the alumina hydrate gel met the requirements being provided for mixed cell, from the conveying easy to material
Angle is set out, and in a preferred embodiment, the separation of solid and liquid and washing unit can include washing subelement, dilution
Subelement, conveying subelement and separation of solid and liquid subelement,
The washing subelement is used for the alumina hydrate gel for collecting the alumina hydrate gel production unit output
Solid phase in solution is simultaneously washed；
The dilution subelement is used to the solid phase of the washing subelement output being diluted with water, obtains slurries；
The conveying subelement is used to the slurries of the dilution subelement output being sent into separation of solid and liquid subelement；
The separation of solid and liquid subelement is used to the slurries carrying out separation of solid and liquid, obtains hydrated alumina wet gel.
The conveying subelement can use conventional various conveying devices, such as conveyer belt.The conveying subelement and institute
Stating washing subelement can integrate, such as integrate in one apparatus, so as to be washed during conveying, carry
High efficiency.Such as：Using the conveyer belt with solid-liquid separation function, while spray is set above the solid-phase material of conveyer belt
Shower device, so as to be washed during transporting and separation of solid and liquid.
The mixed cell includes the assistant feeding device that auxiliary agent is added into hydrated alumina wet gel, in the production system
During system operation, the assistant feeding device adds at least into hydrated alumina wet gel has at least two proton acceptor sites
Compound.
The mixed cell can use conventional mixing arrangement, such as common various mixers, kneader or two
The combination of person.The forming unit can use conventional molding machine, such as：Extrusion device, spraying device, circle rolling device,
Preforming device or two or more combinations.The drying unit can use conventional drying device, and the present invention does not have this
It is particularly limited to.The roasting unit can use conventional calciner, this is also not particularly limited in the present invention.
On the basis of the flow direction of alumina hydrate gel, the production formation system is in separation of solid and liquid and the solid phase of washing unit
Material discharging port is wet by hydrated alumina to being not provided with being enough between the hydrated alumina wet gel input port of mixed cell
The i values of gel are reduced to the dewatering unit of less than 60% (preferably less than 61%).
The water vapour conveying subelement is used in roasting process input water steaming into the container for accommodating material to be roasted
Vapour.The water vapour conveying subelement can be connected with water vapour storage tank, so that defeated into the container in roasting process
Enter water vapour.The water vapour that subelement input is conveyed by the water vapour can be fresh water steam, or dried
The journey water vapour that either roasting process produces can also be the water vapour produced in fresh water vapour and drying or roasting process
Combination.
The production formation system preferably further includes water vapour collector unit, and the water vapour of the water vapour collector unit is defeated
The water vapour output port and/or roasting unit that are used to export the water vapour produced in drying process of inbound port and drying unit
The water vapour output port connection for being used to export the water vapour produced in roasting process, and the water of the water vapour collector unit
Steam output end mouth imports port with the water vapour of water vapour conveying subelement and connects, for collecting drying unit in drying
During or the water vapour that is produced in roasting process of the roasting unit, and at least part water vapour is circulated and is sent into roasting
Burn in unit.In one embodiment, which includes drying unit, the material to be roasted of the roasting unit
When input port is connected with the dried material output port of the drying unit, the drying unit be used for export it is dried
The water vapour output port of the water vapour produced in journey is connected with the water vapour input port of the water vapour collector unit, to connect
The water vapour that drying unit of receiving produces in the drying process.In another embodiment, the roasting unit treats calcining matter
Material input port is connected with the molding output port of the forming unit, and (that is, which does not include dry single
Member), the water vapour output port for being used to export the water vapour produced in roasting process of the roasting unit and the water vapour
The water vapour input port connection of collector unit, to be received in the water vapour produced in roasting process.
In the actual production process, mixing can be added on the basis of existing alumina hydrate gel process units
Unit, forming unit, drying unit and roasting unit, production and molding one so as to fulfill alumina hydrate gel
Change.
According to the fourth aspect of the present invention, the present invention provides a kind of method system as described in third aspect of the present invention
Standby alumina support.
The pore-size distribution of the aluminium oxide formed body described in the 4th aspect is in Unimodal Distribution according to the present invention.Wherein, by pressing
Mercury method measures, and most probable pore size is respectively 4-60nm, is preferably 5-40nm, more preferably 6-20nm, more preferably 7-
15nm。
Aluminium oxide formed body described in 4th aspect according to the present invention, has higher intensity.Usually, according to this hair
The radial direction crushing strength of aluminium oxide formed body described in bright 4th aspect is more than 10N/mm, such as 10-40N/mm, is preferably
15-30N/mm。
According to the fifth aspect of the present invention, the present invention provides second according to the present invention aspect or the 4th aspect
Application of the aluminium oxide formed body as carrier or adsorbent.
Aluminium oxide formed body according to the present invention is particularly suitable as the carrier of loaded catalyst.The supported catalyst
Agent can be commonly used in the art various the catalyst of carrier can be used as using aluminium oxide formed body.Preferably, the catalyst
For the catalyst acted on hydrogenation catalyst.That is, aluminium oxide formed body according to the present invention is particularly suitable as urging with hydrogenation
The carrier of the catalyst of change effect.
Can use various methods commonly used in the art (such as：Dipping) it will be born with the active component that hydrogenation catalyst acts on
It is loaded on aluminium oxide formed body according to the present invention, such as：This can be impregnated by using the aqueous solution containing the active component
The formed body of invention, then the formed body for being loaded with the active component is dried and optional roasting, so as to obtain
Catalyst with hydrogenation catalyst effect.
According to the sixth aspect of the invention, the present invention provides a kind of catalyst with hydrogenation catalyst effect, this is urged
Agent contains the hydrogenation active component of carrier and load on the carrier, wherein, the carrier is according to the present invention second
Aluminium oxide formed body described in a aspect or the 4th aspect.
The hydrogenation active component can be conventional selection.Preferably, the hydrogenation active component is vib metals member
Element and group VIII metallic element.The group VIII metallic element and the vib metals element can be that this area is normal
The various elements with hydrogenation catalyst effect.Preferably, the group VIII metallic element is cobalt and/or nickel, described
Group vib metallic element is molybdenum and/or tungsten.The content of the group VIII metallic element and vib metals element can basis
The concrete application occasion of catalyst makes appropriate choice.For example, it is used for adding for heavy hydrocarbon oil in catalyst according to the invention
During hydrogen processing, on the basis of the total amount of the catalyst, the content of the carrier can be 55-94.5 weight %, be preferably 64-
93 weight %, more preferably 76-88 weight %；In terms of oxide, the content of the group VIII metallic element can be 0.5-
10 weight %, are preferably 1-6 weight %, more preferably 2-4 weight %；In terms of oxide, the vib metals element contains
Amount can be 5-35 weight %, be preferably 6-30 weight %, more preferably 10-20 weight %.
According to the seventh aspect of the present invention, the present invention provides a kind of preparation of the catalyst with hydrogenation catalyst effect
Method, this method are included in supported on carriers hydrogenation active component, wherein, the carrier is to be molded according to the aluminium oxide of the present invention
Body.
The preparation method of catalyst according to the present invention with hydrogenation catalyst effect, preferably further includes and prepares formed body
Step.In this step, formed body is prepared using the method described in second aspect of the present invention or the 4th aspect.
The preparation method of catalyst according to the present invention with hydrogenation catalyst effect, the hydrogenation active component can be
Conventional selection.Preferably, the hydrogenation active component is vib metals element and group VIII metallic element.Described
Group VIII metal element is preferably cobalt and/or nickel, and the vib metals element is preferably molybdenum and/or tungsten.The hydrogenation activity
Load capacity of the component on carrier can make appropriate choice according to the concrete application occasion of catalyst.For example, in preparation
Catalyst be used for hydrocarbon ils hydrotreating when, on the basis of the total amount of the catalyst of preparation, the group VIII metallic element and
The load capacity of vib metals element on the carrier causes group VIII metallic element and in the catalyst that finally prepares
The content of group vib metallic element disclosure satisfy that the requirement described in the 6th aspect of the present invention.
The preparation method of catalyst according to the present invention with hydrogenation catalyst effect, can use commonly used in the art each
Kind method loads the hydrogenation active component on the carrier, such as：Dipping.The dipping can be that saturation impregnates,
It can be excessive dipping.Can be molten by the compound of the compound of the metallic element containing group VIII and the element containing vib metals
Solution forms maceration extract, and the carrier described in the maceration extract in solvent (being usually water).The metallic element containing group VIII
Compound can be catalyst preparation technical field conventional selection, can be selected from group VIII metallic element nitrate,
The chloride of group VIII metallic element, the sulfate of group VIII metallic element, the formates of group VIII metallic element,
The acetate of group VIII metal element, the phosphate of group VIII metallic element, the citrate of group VIII metallic element,
The oxalates of group VIII metal element, the carbonate of group VIII metallic element, group VIII metallic element subcarbonate,
The hydroxide of group VIII metallic element, the phosphate of group VIII metallic element, group VIII metallic element phosphide,
The sulfide of group VIII metallic element, the aluminate of group VIII metallic element, the molybdate of group VIII metallic element,
The tungstates of group VIII metal element and the water-soluble oxide of group VIII metallic element.Specifically, it is described to contain group VIII
The instantiation of the compound of metallic element can include but is not limited to nickel nitrate, nickel sulfate, nickel acetate, basic nickel carbonate, nitre
Sour cobalt, cobaltous sulfate, cobalt acetate, basic cobaltous carbonate, cobalt chloride and nickel chloride.The tool of compound containing vib metals element
Body example can include but is not limited to ammonium molybdate, ammonium paramolybdate, ammonium metatungstate, molybdenum oxide and tungsten oxide.
The preparation method of catalyst according to the present invention with hydrogenation catalyst effect, can be at the same time by hydrogenation active component
Load on the carrier, by several times can also load hydrogenation active component on the carrier.
The preparation method of catalyst according to the present invention with hydrogenation catalyst effect, can be in condition commonly used in the art
The lower carrier for obtaining dipping is dried and optionally roasts.Usually, the condition of the drying includes：Temperature can be
100-200 DEG C, be preferably 110-160 DEG C；When duration can be 1-15 small, when being preferably 2-10 small, more preferably 2-4 is small
When.The condition of the roasting includes：Temperature can be 350-550 DEG C, be preferably 400-500 DEG C；Duration can be that 1-8 is small
When, when being preferably 1-6 small, when more preferably 1.5-3 is small.
According to the eighth aspect of the present invention, the present invention provides a kind of hydrotreating method, this method is included in hydrogenation
Under treatment conditions, hydrocarbon ils is contacted with the catalyst with hydrogenation catalyst effect, wherein, the urging with hydrogenation catalyst effect
Agent is the catalyst described in the 6th aspect of the present invention or the catalysis prepared as the method described in the 7th aspect of the present invention
Agent.
The hydrotreating method of the present invention is not particularly limited for the species and hydroprocessing condition of hydrocarbon ils, can be this
The conventional selection in field.Specifically, the hydrocarbon ils can be various heavy mineral oils, artificial oil or heavy mineral oil and artificial oil
Mixed fraction oil, such as：The hydrocarbon ils can be to be closed selected from crude oil, distillate, solvent-refined oil, slack wax, sweat oil, Fischer-Tropsch
One or more into oil, liquefied coal coil, frivolous coal tar and heavy deasphalted oil.Preferably, the hydrocarbon ils is to contain heavy
The hydrocarbon ils of mineral oil, such as various inferior heavy oils, such as reduced crude, decompression residuum, vacuum gas oil (VGO), wax tailings and coal tar
Deng.The condition of the hydrotreating includes：Temperature can be 300-380 DEG C；In terms of gauge pressure, hydrogen dividing potential drop can be 4-15MPa；Hydrocarbon
When volume space velocity can be 0.5-3 small during the liquid of oil-1。
Hydrotreating method according to the present invention, before hydrogenation reaction is carried out, preferably under the normal condition of this area, in
In the presence of hydrogen, presulfurization is carried out to catalyst, the presulfurization can carry out in hydrogenation reactor, can also be anti-in hydrogenation
Answer and carried out outside device, is not particularly limited.The presulfurization can generally carry out at a temperature of 140-370 DEG C.
The present invention will be described in detail with reference to embodiments, but the scope being not intended to limit the present invention.
In following embodiments and comparative example, the radial direction of the molding prepared using method measure specified in RIPP 25-90
Crushing strength.
In following embodiments and comparative example, measured using following methodsValue：By 10g hydrated aluminas composition at 120 DEG C
It is 240 minutes dry in air atmosphere, the quality through dry composition is denoted as w1, calculated using Formulas IValue,
In following embodiments and comparative example, i values are measured using following methods：By 10g hydrated aluminas wet gel at 120 DEG C
It is 240 minutes dry in air atmosphere, the quality through dry sample is denoted as w2, i values are calculated using Formula II,
In following embodiments and comparative example, the water absorption rate of the formed body prepared using following methods measure：By shaping to be measured
Then body is sieved with 40 the polished standard screens when 120 DEG C of dryings 4 are small, weighs 20g oversizes and (be denoted as sample to be tested
w3), sample to be tested 50g deionized waters are soaked 30 minutes, after filtering, solid phase are drained 5 minutes, what then weighing drained consolidates
The weight of phase (is denoted as w4), calculate water absorption rate with the following formula：
In following embodiments and comparative example, using Kang Ta companies of U.S. Poremaster33 instruments, with reference to GB/T
Mercury injection method specified in 21650.1-2008 measures most probable pore size.
In following embodiments and comparative example, the method with reference to specified in Petrochemical Engineering Analysis method RIPP133-90, in day
The composition of catalyst is measured on 3271 type Xray fluorescence spectrometer of this Liue electrical machinery Industrial Co., Ltd.
Embodiment 1-13 is used to illustrate aluminium oxide formed body of the present invention and preparation method thereof.
Embodiment 1
The hydrated alumina wet gel used in the present embodiment is that (sodium metaaluminate-aluminum sulfate method, is derived from Chinese stone by acid system
Change Chang Ling branch company) prepare alumina hydrate gel solution washed and be obtained by filtration boehmite wet cake (will
Wet cake numbering is SLB-1), after measured, the i values of the wet cake are 78.2%.
(1) wet cake that 5kg numberings are SLB-1 is mixed with beating 1 minute with 500g deionized waters, the slurry that then will be obtained
Liquid is sent into plate and frame type filter-press, and the pressure of sheet frame is adjusted to 0.7MPa and is kept for 15 minutes, and obtaining wet cake, (numbering is
LB-1).After measured, the i values for the wet cake that numbering is LB-1 are 62%.
(2) wet cake that 300g numberings are LB-1 is placed in beaker, adds 4.5g hydroxyethylmethylcelluloses (purchased from upper
Hai Huiguang Fine Chemical Co., Ltd, similarly hereinafter) and 1.5g sesbania powders (content of galactomannans is 85 weight %, purchased from north
Capital chemical reagents corporation), using mechanical agitator stirring after ten minutes, obtain the hydrated alumina composition of the present invention, its property
Matter is listed in table 1.
(3) the hydrated alumina composition for preparing step (2) utilizes Ф 2.0mm's on F-26 type double screw extruders
Circular orifice carries out extrusion.Wherein, extrusion process is smooth, extrudate surface Glabrous thorn.
(4) extrudate is cut into the wet bar that length is about 6mm, wet bar is sent into tube furnace, with 100 DEG C/h
Heating rate raises temperature to 500 DEG C from environment temperature (for 25 DEG C), and when constant temperature 4 is small at such a temperature, wet bar is sent into and is managed
Blown after formula stove with the 14L/ minutes entrances from tube furnace to the inner space of tube furnace, wherein, the air quantity of 12L/ minute for from
The circulated air (amount of water vapour is 8L/ minutes, is 0.07L/ (ming moldings)) of the outlet output of tube furnace, remaining 2L/
The air quantity of minute is air.It is out-of-blast after the completion of constant temperature, and the temperature of tube furnace is down to environment temperature naturally, take out solid
Body material obtains aluminium oxide formed body according to the present invention, its nature parameters is listed in table 1.
Embodiment 2
Aluminium oxide formed body is prepared using method same as Example 1, unlike, without using sesbania in step (2)
Powder, the dosage of hydroxyethylmethylcellulose is 5.8g.The nature parameters of the aluminium oxide formed body of preparation are listed in table 1.
Embodiment 3
Aluminium oxide formed body is prepared using method same as Example 1, unlike, without using hydroxyl second in step (2)
Ylmethyl cellulose, the dosage of sesbania powder is 6.8g.The nature parameters of the aluminium oxide formed body of preparation are listed in table 1.
Embodiment 4
Formed body and catalyst are prepared using method same as Example 1, unlike, in step (2), in addition hydroxyl
When ethylmethylcellulose and sesbania powder, 3g nitric acid (HNO is also added3Content be 65 weight %).The aluminium oxide shaping of preparation
The nature parameters of body are listed in table 1.
Comparative example 1
Aluminium oxide formed body is prepared using method same as Example 1, unlike, it is not by tubular type in step (3)
The airflow circulating of the outlet output of stove is sent into tube furnace, but with the 15L/ minutes entrances from tube furnace to the inside of tube furnace
Send air in space.The nature parameters of the alumina support of preparation are listed in table 2.
Comparative example 2
(1) by 500g numberings be LB-1 wet cake in 80 DEG C, air atmosphere it is dry 2 it is small when, obtain boehmite
Powder, the i values of the boehmite powder are 50%.The boehmite powder (is placed in environment temperature (25-30 DEG C) and sealing condition
In sealed plastic bag) under place 72 it is small when, do not detected after placement and form gibbsite.
(2) the boehmite powder for preparing step (1) utilizes the circle of Ф 2.0mm on F-26 type double screw extruders
Orifice plate carries out extrusion.Wherein, extruder caloric value is larger during extrusion (it is hot to show as banded extruder fuselage, has a large amount of hot gas to emit
Go out), and extruder Frequent trip during extrusion, extrudate surface are jagged.
(3) extrudate is cut into the wet bar and the use method system identical with 2 step of embodiment (4) that length is about 6mm
Standby aluminium oxide formed body, its nature parameters are listed in table 1.
Comparative example 3
(1) by the wet cake that 500g numberings are LB-1 at a temperature of 90 DEG C, in air atmosphere it is dry 3 it is small when, intended
Boehmite powder, the i values of the boehmite powder are 40%.The boehmite powder is in environment temperature (25-30 DEG C) and closes
When placement 72 is small under condition (being placed in sealed plastic bag), is not detected after placement and form gibbsite.
(2) boehmite powder prepared by 190g steps (1) is placed in beaker, adds 4.5g hydroxyethylmethylcelluloses
(with embodiment 1) and 1.5g sesbania powders (with embodiment 1), using mechanical agitator stirring after ten minutes, obtain boehmite
Composition.
(3) the boehmite composition for preparing step (2) utilizes Ф 2.0mm's on F-26 type double screw extruders
Circular orifice carries out extrusion.Wherein, extruder Frequent trip during extrusion, extrudate surface are smooth.
(4) extrudate is cut into the wet bar and the use method system identical with 2 step of embodiment (4) that length is about 6mm
Standby aluminium oxide formed body, its nature parameters are listed in table 1.
Comparative example 4
(1) 190g is placed in beaker using boehmite powder prepared by the method identical with 3 step of comparative example (1),
Add 4.5g hydroxyethylmethylcelluloses (with embodiment 1), 1.5g sesbania powders (with embodiment 1) and 6g nitric acid (HNO3Concentration
For 65 weight %), using mechanical agitator stirring after ten minutes, obtain boehmite composition.
(2) the boehmite composition for preparing step (1) utilizes Ф 2.0mm's on F-26 type double screw extruders
Circular orifice carries out extrusion.Wherein, extrusion process is smooth, and extrudate surface is smooth.
(3) extrudate is cut into the wet bar and the use method system identical with 2 step of embodiment (4) that length is about 6mm
Standby aluminium oxide formed body, its nature parameters are listed in table 1.
Comparative example 5
Hydrated alumina composition is prepared using method same as Example 1, unlike, without using hydroxyethyl methyl
Cellulose and sesbania powder, but with 6.0g paraffin.As a result the hydrated alumina composition prepared can not carry out extrusion molding.
Comparative example 6
Hydrated alumina composition is prepared using method same as Example 1, unlike, without using hydroxyethyl methyl
Cellulose and sesbania powder, but with 6.0g wood powders.As a result the hydrated alumina composition prepared can not carry out extrusion molding.
Comparative example 7
Will number be LB-1 wet cake be sent directly into F-26 type double screw extruders utilize Ф 2.0mm circular orifice
Extrusion is carried out, as a result can not carry out extrusion molding.
Embodiment 5
(1) wet cake that 300g numberings are LB-1 is placed in beaker, adds 2.6g hydroxypropyl methyl celluloses and (be purchased from Zhejiang
Jiang Haishen Chemical Co., Ltd.s, similarly hereinafter) and 3.5g sesbania powders (content of galactomannans is 85 weight %), stirred using machinery
Mix device stirring after ten minutes, obtain the hydrated alumina composition of the present invention, its property is listed in table 1.
(2) the hydrated alumina composition for preparing step (1) is in SK132S/4 types single screw extrusion machine (U.S. BONNT
Company system) on using the orifice plate that the circular and middle cylinder with a 1.5mm for being Ф 4.5mm by overall diameter collectively constitutes into
Row extrusion.Wherein, extrusion process is smooth, extrudate (for Raschig ring) surface Glabrous thorn.
(3) extrudate is cut into the wet bar that length is about 6mm, wet bar is sent into tube furnace, with 200 DEG C/h
Heating rate raises temperature to 850 DEG C from environment temperature (for 25 DEG C), and when constant temperature 3 is small at such a temperature, wet bar is sent into and is managed
Blown after formula stove with the 16L/ minutes entrances from tube furnace to the inner space of tube furnace, wherein, the air quantity of 12L/ minute for from
The circulated air (amount of water vapour is 6L/ minutes, is 0.05L/ (ming moldings)) of the outlet output of tube furnace, remaining 4L/
The air quantity of minute is air.It is out-of-blast after the completion of constant temperature, and the temperature of tube furnace is down to environment temperature naturally, take out solid
Body material obtains aluminium oxide formed body according to the present invention, its nature parameters is listed in table 1.
Embodiment 6
(1) wet cake that 300g numberings are LB-1 is placed in beaker, adds 2g methylcellulose, 1.1g hydroxypropyl methyls
Cellulose and 4g sesbania powders (content of galactomannans is 85 weight %), using mechanical agitator stirring after ten minutes, obtain
To the hydrated alumina composition of the present invention, its nature parameters is listed in table 1.
(2) the hydrated alumina composition for preparing step (1) utilizes Ф 3.0mm's on F-26 type double screw extruders
Cloverleaf pattern orifice plate carries out extrusion.Wherein, extrusion process is smooth, extrudate surface Glabrous thorn.
(3) extrudate is cut into the wet bar that length is about 8mm, wet bar is sent into tube furnace, with 150 DEG C/h
Heating rate raises temperature to 900 DEG C from environment temperature (for 25 DEG C), and when constant temperature 2 is small at such a temperature, wet bar is sent into and is managed
Blown after formula stove with the 12L/ minutes entrances from tube furnace to the inner space of tube furnace, wherein, the air quantity of 9L/ minutes is from pipe
The circulated air (amount of water vapour is 5L/ minutes, is 0.04L/ (ming moldings)) of the outlet output of formula stove, remaining 3L/ points
The air quantity of clock is air.It is out-of-blast after the completion of constant temperature, and the temperature of tube furnace is down to environment temperature naturally, take out solid
Material obtains aluminium oxide formed body according to the present invention, its nature parameters is listed in table 1.
Embodiment 7
(1) wet cake that 300g numberings are LB-1 is placed in beaker, adds 2.2g hydroxyethylmethylcelluloses and 2.1g
Hydroxypropyl methyl cellulose, using mechanical agitator stirring after ten minutes, obtains the hydrated alumina composition of the present invention, its property
Matter parameter is listed in table 1.
(2) the hydrated alumina composition for preparing step (1) utilizes Ф 1.8mm's on F-26 type double screw extruders
Dish-shaped orifice plate carries out extrusion.Wherein, extrusion process is smooth, extrudate surface Glabrous thorn.
(3) extrudate is cut into the wet bar that length is about 6mm, wet bar is sent into tube furnace, with 200 DEG C/h
Heating rate raises temperature to 800 DEG C from environment temperature (for 25 DEG C), and when constant temperature 2 is small at such a temperature, wet bar is sent into and is managed
Blown after formula stove with the 15L/ minutes entrances from tube furnace to the inner space of tube furnace, wherein, the air quantity of 10L/ minute for from
The circulated air (amount of water vapour is 6L/ minutes, is 0.05L/ (ming moldings)) of the outlet output of tube furnace, remaining 5mL/
The air quantity of minute is air.It is out-of-blast after the completion of constant temperature, and the temperature of tube furnace is down to environment temperature naturally, take out solid
Body material obtains aluminium oxide formed body according to the present invention, its nature parameters is listed in table 1.
Embodiment 8
(1) wet cake that 5kg numberings are SLB-1 is sent into plate and frame type filter-press, the pressure of sheet frame is adjusted to
1.3MPa is simultaneously kept for 20 minutes, the filter cake 10 minutes in sheet frame is then swept with the wind with pressure of 0.5MPa, sheet frame pressure release obtains wet
Filter cake (numbering LB-2).The i values of the wet cake are 61.1%.
(2) wet cake that 1000g numberings are LB-2 is placed in beaker, adds 16g hydroxypropyl methyl celluloses and 20g fields
Cyanines powder (content of galactomannans is 85 weight %, purchased from Beijing chemical reagents corporation), 10 are stirred using mechanical agitator
After minute, the hydrated alumina composition of the present invention is obtained, its nature parameters is listed in table 1.
(3) the hydrated alumina composition for preparing step (1) utilizes Ф 2.4mm's on F-26 type double screw extruders
Dish-shaped orifice plate carries out extrusion.Wherein, extrusion process is smooth, extrudate surface Glabrous thorn.
(4) extrudate is cut into the wet bar that length is about 6mm, wet bar is sent into tube furnace, with 150 DEG C/h
Heating rate raises temperature to 700 DEG C from environment temperature (for 25 DEG C), and when constant temperature 3 is small at such a temperature, wet bar is sent into and is managed
Blown after formula stove with the 12L/ minutes entrances from tube furnace to the inner space of tube furnace, wherein, the air quantity of 10L/ minute for from
The circulated air (amount of water vapour is 5L/ minutes, is 0.1L/ (ming moldings)) of the outlet output of tube furnace, remaining 2L/ points
The air quantity of clock is air.It is out-of-blast after the completion of constant temperature, and the temperature of tube furnace is down to environment temperature naturally, take out solid
Material obtains aluminium oxide formed body according to the present invention, its nature parameters is listed in table 1.
Embodiment 9
The hydrated alumina wet gel used in the present embodiment is by CO2Method (sodium aluminate-CO2Method, is derived from Shanxi Province Shan County
Emerging great catalyst new material Co., Ltd) the alumina hydrate gel solution thin water aluminium of plan that is washed and be obtained by filtration for preparing
Stone wet cake (being SLB-2 by wet cake numbering), after measured, the i values of the wet cake are 65.3%.
(1) wet cake that 1000g numberings are SLB-2 is placed in beaker, then adds 16g methylcellulose and 20g fields
Cyanines powder (content of galactomannans is 80 weight %), using mechanical agitator stirring after ten minutes, obtained mixture is
The hydrated alumina composition of the present invention, its nature parameters are listed in table 1.
(2) the hydrated alumina composition for preparing step (1) utilizes Ф 2.4mm's on F-26 type double screw extruders
Dish-shaped orifice plate carries out extrusion, and extrusion process is smooth, extrudate surface Glabrous thorn.
(3) extrudate is cut into the wet bar that length is about 5mm, wet bar is sent into tube furnace, with 100 DEG C/h
Heating rate raises temperature to 550 DEG C from environment temperature (for 25 DEG C), and when constant temperature 3 is small at such a temperature, wet bar is sent into and is managed
Blown after formula stove with the 16L/ minutes entrances from tube furnace to the inner space of tube furnace, wherein, the air quantity of 12L/ minute for from
The circulated air (amount of water vapour is 7L/ minutes, is 0.2L/ (ming moldings)) of the outlet output of tube furnace, remaining 4L/ points
The air quantity of clock is air.It is out-of-blast after the completion of constant temperature, and the temperature of tube furnace is down to environment temperature naturally, take out solid
Material obtains aluminium oxide formed body according to the present invention, its nature parameters is listed in table 1.
Embodiment 10
The hydrated alumina wet gel used in the present embodiment is that (sodium aluminate kind point-score is derived from Chalco Shandong point public affairs
Department) the alumina hydrate gel solution gibbsite wet cake that is washed and be obtained by filtration for preparing (compiles the wet cake
Number it is SLB-3), after measured, the i values of the wet cake are 70%.
(1) it is that SLB-3 and 1000g water is mixed with beating by 5000g numberings, obtained slurries is pressed into plate and frame type filter-press
In, the sheet frame pressure of plate and frame filter is adjusted to 0.9MPa and is kept for 3 minutes, then sweeps plate with the wind with pressure of 0.6MPa
Filter cake in frame 5 minutes, sheet frame pressure release obtain 2.5kg gibbsite wet cakes, and the i values of the wet cake are 60.8 weight %.
(2) wet cake obtained through 1000g steps (1) is placed in beaker, then adds 10g methylcellulose and 20g fields
Cyanines powder (content of galactomannans is 80 weight %), using mechanical agitator stirring after ten minutes, obtained mixture is
The hydrated alumina composition of the present invention, its nature parameters are listed in table 1.
(3) the hydrated alumina composition for preparing step (1) utilizes Ф 2.4mm's on F-26 type double screw extruders
Dish-shaped orifice plate carries out extrusion.Wherein, extrusion process is smooth, extrudate surface Glabrous thorn.
(4) extrudate is cut into the wet bar that length is about 6mm, wet bar is sent into tube furnace, with 200 DEG C/h
Heating rate raises temperature to 1000 DEG C from environment temperature (for 25 DEG C), and when constant temperature 2 is small at such a temperature, wet bar is sent into and is managed
Blown after formula stove with the 15L/ minutes entrances from tube furnace to the inner space of tube furnace, wherein, the air quantity of 10L/ minute for from
The circulated air (amount of water vapour is 6L/ minutes, is 0.15L/ (ming moldings)) of the outlet output of tube furnace, remaining 5L/
The air quantity of minute is air.It is out-of-blast after the completion of constant temperature, and the temperature of tube furnace is down to environment temperature naturally, take out solid
Body material obtains aluminium oxide formed body according to the present invention, its nature parameters is listed in table 1.
Embodiment 11
The hydrated alumina wet gel used in the present embodiment is derived from the neat cyclopentadienyl catalyst Co., Ltd of Shandong Zibo, be by
Boehmite dry powder (butt is 70 weight %) prepared by 1000g acid systems (sodium aluminate-aluminum sulfate method) is in 700 DEG C, air gas
When roasting 3 is small in atmosphere, 700g aluminium oxide is obtained, 700g aluminium oxide is placed in 10L autoclaves, stirred with 5L deionized waters
After uniformly, autoclave is sealed, 6h is reacted under 150 DEG C, pressure itself, after reaction, by the temperature of autoclave
After being down to room temperature (for 25 DEG C), the slurries that reaction is obtained are sent into plate and frame type filter-press, by the sheet frame pressure of plate and frame filter
Power is adjusted to 0.5MPa and is kept for 10 minutes, and the filter cake 3 minutes in sheet frame, sheet frame pressure release are then swept with the wind with pressure of 10MPa
Obtain the hydrated alumina wet cake LB-3 of the present invention.After measured, the thing of the wet cake is mutually boehmite, the i of the wet cake
It is worth for 63%.
(1) wet cake that 300g numberings are LB-3 is placed in beaker, then adds 3.8g methylcellulose and 6g sesbanias
Powder (content of galactomannans is 85 weight %), using mechanical agitator stirring after ten minutes, obtained mixture are this
The hydrated alumina composition of invention, its nature parameters are listed in table 1.
(2) the hydrated alumina composition for preparing step (1) utilizes Ф 2.4mm's on F-26 type double screw extruders
Dish-shaped orifice plate carries out extrusion.Wherein, extrusion process is smooth, extrudate surface Glabrous thorn.
(3) extrudate is cut into the wet bar that length is about 6mm, wet bar is sent into tube furnace, with 120 DEG C/h
Heating rate raises temperature to 600 DEG C from environment temperature (for 25 DEG C), and when constant temperature 4 is small at such a temperature, wet bar is sent into and is managed
Blown after formula stove with the 16L/ minutes entrances from tube furnace to the inner space of tube furnace, wherein, the air quantity of 12L/ minute for from
The circulated air (amount of water vapour is 8L/ minutes, is 0.07L/ (ming moldings)) of the outlet output of tube furnace, remaining 4L/
The air quantity of minute is air.It is out-of-blast after the completion of constant temperature, and the temperature of tube furnace is down to environment temperature naturally, take out solid
Body material obtains aluminium oxide formed body according to the present invention, its nature parameters is listed in table 1.
Embodiment 12
The hydrated alumina wet gel used in the present embodiment uses《Petroleum journal (PETROLEUM PROCESSING)》, volume 10 the 4th
Method in the article " new method of preparing alumina by hydrolysis of low carbon aluminum alkoxide " that phase delivers described in " one, test method " part
Prepare, wherein, when ageing time is 12 small, after aging terminates and steams isopropyl alcohol and water, 500g water is added, uses mechanical agitation
Device stirs 1 minute, and slurries are pressed into plate and frame filter, and the pressure of sheet frame is adjusted to 0.7MPa, and extrusion time is 8 points
Clock, the filter cake 4 minutes in sheet frame is then swept with the wind with pressure of 7MPa, obtains 200g wet cakes (numbering LB-4).After measured,
The thing of the wet cake is mutually boehmite, and the i values of the wet cake are 65.2%.
(1) wet cake that 200g numberings are LB-4 is placed in beaker, then adds 2.8g methylcellulose and 4.5g fields
Cyanines powder (content of galactomannans is 80 weight %), using mechanical agitator stirring after ten minutes, obtained mixture is
The hydrated alumina composition of the present invention, its nature parameters are listed in table 1.
(2) the hydrated alumina composition for preparing step (1) utilizes Ф 2.4mm's on F-26 type double screw extruders
Dish-shaped orifice plate carries out extrusion.Wherein, extrusion process is smooth, extrudate surface Glabrous thorn.
(3) extrudate is cut into the wet bar that length is about 6mm, wet bar is sent into tube furnace, with 100 DEG C/h
Heating rate raises temperature to 550 DEG C from environment temperature (for 25 DEG C), and when constant temperature 3 is small at such a temperature, wet bar is sent into and is managed
Blown after formula stove with the 14L/ minutes entrances from tube furnace to the inner space of tube furnace, wherein, the air quantity of 12L/ minute for from
The circulated air (amount of water vapour is 7L/ minutes, is 0.05L/ (ming moldings)) of the outlet output of tube furnace, remaining 2L/
The air quantity of minute is air.It is out-of-blast after the completion of constant temperature, and the temperature of tube furnace is down to environment temperature naturally, take out solid
Body material obtains aluminium oxide formed body according to the present invention, its nature parameters is listed in table 1.
Embodiment 13
Aluminium oxide formed body is prepared using the method identical with embodiment 12, unlike, in step (3), be not by from
Tube furnace outlet output circulated air be sent into tube furnace inside, but by the fresh water vapour produced by steam generator with
The gaseous mixture of air is sent into tube furnace, wherein, the feeding amount of water vapour is 8L/min.The property of the aluminium oxide formed body of preparation
Parameter is listed in table 1.
Table 1
1：When placement 72 is small under environment temperature (25-30 DEG C) and sealing condition (being placed in sealed plastic bag), after placement
The content of gibbsite in composition is compared with the increase rate before placement.
Embodiment 1-13's as a result, it was confirmed that the present invention by hydrated alumina wet gel without being dried to dry glue powder or partial desiccation
Rubber powder, but directly mixed with the compound with least two proton acceptor sites, obtained mixture can be used directly
In shaping, and obtained formed body has the intensity of higher, is made so as to avoid existing with dry glue powder or semiarid rubber powder
The problem of existing operating environment is severe when preparing formed body for starting material, high energy consumption and the formed body intensity for preparing is not high.
EXPERIMENTAL EXAMPLE 1-11 is used to illustrate the catalyst and its preparation side according to the present invention with hydrogenation catalyst effect
Method.
EXPERIMENTAL EXAMPLE 1
Molybdenum oxide and basic cobaltous carbonate are dispersed in water, form maceration extract, wherein, MoO3Concentration be 197.4g/L,
The concentration of basic cobaltous carbonate is counted as 47.6g/L using CoO.With the maceration extract, saturation dipping is prepared in fact under environment temperature (for 25 DEG C)
Apply example 1 preparation aluminium oxide formed body 1 it is small when.Alumina dry bar through dipping is dry in air atmosphere under 120 DEG C, normal pressure
2 it is small when after, then under 400 DEG C, normal pressure in air atmosphere roasting 3 it is small when so that obtain according to the present invention have hydrogenation
The catalyst C-1 of catalytic action, its composition are listed in table 2.
EXPERIMENTAL EXAMPLE 2
Catalyst is prepared using the method identical with EXPERIMENTAL EXAMPLE 1, unlike, using the oxidation of the preparation of embodiment 2
Aluminium formed body, the composition of the catalyst C-2 of preparation are listed in table 2.
EXPERIMENTAL EXAMPLE 3
Catalyst is prepared using the method identical with EXPERIMENTAL EXAMPLE 1, unlike, using the oxidation of the preparation of embodiment 3
Aluminium formed body, the composition of the catalyst C-3 of preparation are listed in table 2.
EXPERIMENTAL EXAMPLE 4
Catalyst is prepared using the method identical with EXPERIMENTAL EXAMPLE 1, unlike, using the oxidation of the preparation of embodiment 4
Aluminium formed body, the composition of the catalyst C-4 of preparation are listed in table 2.
Experimental comparison's example 1
Catalyst is prepared using the method identical with EXPERIMENTAL EXAMPLE 1, unlike, using the oxidation of the preparation of comparative example 1
Aluminium formed body, the composition of the catalyst DC-1 of preparation are listed in table 2.
Experimental comparison's example 2
Catalyst is prepared using the method identical with EXPERIMENTAL EXAMPLE 1, unlike, using the oxidation of the preparation of comparative example 2
Aluminium formed body, the composition of the catalyst DC-2 of preparation are listed in table 2.
Experimental comparison's example 3
Catalyst is prepared using the method identical with EXPERIMENTAL EXAMPLE 1, unlike, using the oxidation of the preparation of comparative example 3
Aluminium formed body, the composition of the catalyst DC-3 of preparation are listed in table 2.
Experimental comparison's example 4
Catalyst is prepared using the method identical with EXPERIMENTAL EXAMPLE 1, unlike, using the oxidation of the preparation of comparative example 4
Aluminium formed body, the composition of the catalyst DC-4 of preparation are listed in table 2.
EXPERIMENTAL EXAMPLE 5
Molybdenum oxide and basic cobaltous carbonate are dispersed in water, form maceration extract, wherein, MoO3Concentration be 141.2g/L,
The concentration of basic cobaltous carbonate is counted as 33.6g/L using CoO.With the maceration extract, saturation dipping is prepared in fact under environment temperature (for 25 DEG C)
Apply example 5 preparation aluminium oxide formed body 1 it is small when.Alumina dry bar through dipping is dry in air atmosphere under 120 DEG C, normal pressure
2 it is small when after, then under 400 DEG C, normal pressure in air atmosphere roasting 3 it is small when so that obtain according to the present invention have hydrogenation
The catalyst C-5 of catalytic action, its composition are listed in table 2.
EXPERIMENTAL EXAMPLE 6
Molybdenum oxide and basic nickel carbonate are dispersed in water, form maceration extract, wherein, with MoO3Meter molybdenum oxide concentration be
160g/L, the concentration of basic nickel carbonate is counted as 40g/L using NiO.With the maceration extract, saturation impregnates under environment temperature (for 25 DEG C)
When aluminium oxide formed body 1 prepared by preparation embodiment 6 is small.Alumina dry bar through dipping is under 150 DEG C, normal pressure in air atmosphere
After when middle drying 1.5 is small, when then roasting 2 is small in air atmosphere under 420 DEG C, normal pressure, so as to obtain according to the present invention
Catalyst C-6 with hydrogenation catalyst effect, its composition are listed in table 2.
EXPERIMENTAL EXAMPLE 7
Molybdenum oxide and basic nickel carbonate are dispersed in water, form maceration extract, wherein, with MoO3Meter molybdenum oxide concentration be
160g/L, the concentration of basic nickel carbonate is counted as 40g/L using NiO.With the maceration extract, saturation impregnates under environment temperature (for 25 DEG C)
When aluminium oxide formed body 1 prepared by preparation embodiment 7 is small.Alumina dry bar through dipping is under 160 DEG C, normal pressure in air atmosphere
After when middle drying 1 is small, when then roasting 1.5 is small in air atmosphere under 460 DEG C, normal pressure, so as to obtain according to the present invention
Catalyst C-7 with hydrogenation catalyst effect, its composition are listed in table 2.
EXPERIMENTAL EXAMPLE 8
Molybdenum oxide and basic nickel carbonate are dispersed in water, form maceration extract, wherein, with MoO3Concentration be 238.4g/
L, the concentration of basic nickel carbonate is counted as 57.5g/L using NiO.With the maceration extract, under environment temperature (for 25 DEG C) prepared by saturation dipping
When aluminium oxide formed body 1 prepared by embodiment 8 is small.Alumina dry bar through dipping is done under 120 DEG C, normal pressure in air atmosphere
It is dry 2 it is small when after, then under 400 DEG C, normal pressure in air atmosphere roasting 3 it is small when so that obtain according to the present invention have plus
The catalyst C-8 of hydrogen catalysis effect, its composition are listed in table 2.
EXPERIMENTAL EXAMPLE 9
Molybdenum oxide and basic nickel carbonate are dispersed in water, form maceration extract, wherein, with MoO3Meter molybdenum oxide concentration be
160g/L, the concentration of basic nickel carbonate is counted as 40g/L using NiO.With the maceration extract, saturation impregnates under environment temperature (for 25 DEG C)
When aluminium oxide formed body 1 prepared by preparation embodiment 9 is small.Alumina dry bar through dipping is under 120 DEG C, normal pressure in air atmosphere
After when middle drying 3 is small, when then roasting 2 is small in air atmosphere under 480 DEG C, normal pressure, so as to be had according to the present invention
There is the catalyst C-9 that hydrogenation catalyst acts on, its composition is listed in table 2.
EXPERIMENTAL EXAMPLE 10
Molybdenum oxide and basic nickel carbonate are dispersed in water, form maceration extract, wherein, with MoO3Meter molybdenum oxide concentration be
160g/L, the concentration of basic nickel carbonate is counted as 40g/L using NiO.With the maceration extract, saturation impregnates under environment temperature (for 25 DEG C)
When aluminium oxide formed body 1 prepared by preparation embodiment 12 is small.Alumina dry bar through dipping is under 110 DEG C, normal pressure in air gas
After when drying 3 is small in atmosphere, when then roasting 3 is small in air atmosphere under 460 DEG C, normal pressure, so as to obtain according to the present invention
Catalyst C-10 with hydrogenation catalyst effect, its composition are listed in table 2.
EXPERIMENTAL EXAMPLE 11
Catalyst is prepared using the method identical with EXPERIMENTAL EXAMPLE 10, unlike, using the oxygen of the preparation of embodiment 13
Change aluminium formed body.Catalyst C-11 is prepared, its composition is listed in table 2.
Table 2
| Numbering | Carrier source | Catalyst is numbered | NiO (wt%) | CoO (wt%) | MoO3(wt%) |
| EXPERIMENTAL EXAMPLE 1 | Embodiment 1 | C-1 | / | 3.5 | 14.5 |
| EXPERIMENTAL EXAMPLE 2 | Embodiment 2 | C-2 | / | 3.5 | 14.5 |
| EXPERIMENTAL EXAMPLE 3 | Embodiment 3 | C-3 | / | 3.5 | 14.5 |
| EXPERIMENTAL EXAMPLE 4 | Embodiment 4 | C-4 | / | 3.5 | 14.5 |
| Experimental comparison's example 1 | Comparative example 1 | DC-1 | / | 3.5 | 14.5 |
| Experimental comparison's example 2 | Comparative example 2 | DC-2 | / | 3.5 | 14.5 |
| Experimental comparison's example 3 | Comparative example 3 | DC-3 | / | 3.5 | 14.5 |
| Experimental comparison's example 4 | Comparative example 4 | DC-4 | / | 3.5 | 14.5 |
| EXPERIMENTAL EXAMPLE 5 | Embodiment 5 | C-5 | / | 2.5 | 10.5 |
| EXPERIMENTAL EXAMPLE 6 | Embodiment 6 | C-6 | 3.0 | / | 11.0 |
| EXPERIMENTAL EXAMPLE 7 | Embodiment 7 | C-7 | 3.1 | / | 11.2 |
| EXPERIMENTAL EXAMPLE 8 | Embodiment 8 | C-8 | 3.5 | / | 14.5 |
| EXPERIMENTAL EXAMPLE 9 | Embodiment 9 | C-9 | 2.2 | / | 10.1 |
| EXPERIMENTAL EXAMPLE 10 | Embodiment 12 | C-10 | 2.1 | / | 10.0 |
| EXPERIMENTAL EXAMPLE 11 | Embodiment 13 | C-11 | 2.9 | / | 11.1 |
Testing example 1-11
The catalytic performance of the EXPERIMENTAL EXAMPLE 1-11 catalyst prepared is evaluated using following methods, experimental result exists
Listed in table 3.
The feedstock oil used is reduced crude, and the mass content of its nickel is 13.7ppm, and the mass content of vanadium is 34.7ppm,
Sulfur content is 3.6 weight %, and nitrogen content is 0.22 weight %, and carbon residue is 12.7 weight %.
The particle of catalyst breakage into diameter 2-3mm are fitted into reactor, feedstock oil is passed through and is reacted, wherein, instead
It is 380 DEG C, hydrogen dividing potential drop 14MPa to answer temperature, and the volume space velocity of feedstock oil is 0.6h-1。
The method with reference to specified in Petrochemical Engineering Analysis method RIPP62-90, using the sulfur content in coulometry measure oil；
With reference to method specified in GB/T17144, the carbon residue in measure oil, the instrument used for ALCOR companies of the U.S. MCRT-160
The micro carbon residue analyzer of type；The content of metallic nickel and vanadium uses inductive coupling plasma emission spectrograph (ICP- in oil sample
AES) (instrument is U.S.'s PE companies PE-5300 type plasma quantometers to measure, and specific method is shown in Petrochemical Engineering Analysis side
Method RIPP124-90)；The method with reference to specified in Petrochemical Engineering Analysis method RIPP63-90, using in coulometry measure oil
Nitrogen content.According to measurement result, the removal efficiency of impurity is calculated according to the following formula, wherein, demetallization per refers to the de- of nickel and vanadium
Except rate：
Test comparison example 1-4
Using the method identical with testing example 1-11 to Experimental comparison example 1-4 prepare catalyst catalytic performance into
Row evaluation, is as a result listed in table 3.
Table 3
| Numbering | Carrier source | Catalyst is numbered | Desulfurization degree/% | Denitrification percent/% | Demetallization per/% | De- carbon yield/% |
| EXPERIMENTAL EXAMPLE 1 | Embodiment 1 | C-1 | 87.5 | 43.5 | 73.5 | 58.3 |
| EXPERIMENTAL EXAMPLE 2 | Embodiment 2 | C-2 | 84.4 | 40.6 | 70.3 | 54.6 |
| EXPERIMENTAL EXAMPLE 3 | Embodiment 3 | C-3 | 83.9 | 40.8 | 70.7 | 53.9 |
| EXPERIMENTAL EXAMPLE 4 | Embodiment 4 | C-4 | 85.1 | 41.3 | 71.1 | 56.2 |
| Experimental comparison's example 1 | Comparative example 1 | DC-1 | 80.1 | 39.7 | 68.5 | 50.4 |
| Experimental comparison's example 2 | Comparative example 2 | DC-2 | 78.3 | 34.0 | 64.1 | 47.3 |
| Experimental comparison's example 3 | Comparative example 3 | DC-3 | 78.9 | 34.8 | 63.0 | 46.4 |
| Experimental comparison's example 4 | Comparative example 4 | DC-4 | 79.5 | 35.9 | 62.7 | 45.0 |
| EXPERIMENTAL EXAMPLE 5 | Embodiment 5 | C-5 | 85.7 | 42.6 | 72.0 | 54.0 |
| EXPERIMENTAL EXAMPLE 6 | Embodiment 6 | C-6 | 85.6 | 43.0 | 73.1 | 55.2 |
| EXPERIMENTAL EXAMPLE 7 | Embodiment 7 | C-7 | 86.0 | 43.8 | 72.7 | 55.0 |
| EXPERIMENTAL EXAMPLE 8 | Embodiment 8 | C-8 | 86.2 | 42.1 | 74.0 | 58.6 |
| EXPERIMENTAL EXAMPLE 9 | Embodiment 9 | C-9 | 82.1 | 40.9 | 70.1 | 52.1 |
| EXPERIMENTAL EXAMPLE 10 | Embodiment 12 | C-10 | 83.1 | 41.0 | 70.6 | 55.6 |
| EXPERIMENTAL EXAMPLE 11 | Embodiment 13 | C-11 | 84.6 | 41.4 | 70.1 | 52.6 |
Testing example 1-11's as a result, it was confirmed that catalyst according to the invention has higher catalytic activity, can be effective
Ground reduces the impurity content of heavy hydrocarbon oil.
The preferred embodiment of the present invention described in detail above, still, during present invention is not limited to the embodiments described above
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (41)
1. a kind of preparation method of aluminium oxide formed body, this method comprise the following steps：
(1) a kind of hydrated alumina composition is molded, obtains molding, the hydrated alumina composition contains hydration
Aluminium oxide and the compound with least two proton acceptor sites,
The compositionIt is worth for less than 1.8, it is describedValue is measured using following methods：By composition described in 10g 120 DEG C in
It is 240 minutes dry in air atmosphere, the quality through dry composition is denoted as w1, calculated using Formulas IValue,
Alternatively, (2) molding that step (1) obtains is dried, and obtains through dry molding；
(3) in the presence of water vapor, the molding or step (2) step (1) obtained obtain through dry molding
Roasted in oxygen-containing atmosphere.
It is 2. described to have at least relative to hydrated alumina described in 100 parts by weight according to the method described in claim 1, wherein
The content of the compound in two proton acceptor sites is 1-25 parts by weight, is preferably 2-20 parts by weight, more preferably 3-15 weight
Part, it is more preferably 3.5-10 parts by weight.
3. method according to claim 1 or 2, wherein, in the compound with least two proton acceptor sites,
Proton acceptor site is to be formed with water more than one or both of F, O and N of hydrogen bond；
Preferably, the compound with least two proton acceptor sites is the compound containing hydroxyl in molecular structure；
It is highly preferred that the compound with least two proton acceptor sites is polyhydroxy organic compound；
It is further preferred that the compound with least two proton acceptor sites is polysaccharide and/or the etherate of polysaccharide；
It is further preferred that the compound with least two proton acceptor sites is galactan, mannosan, half
More than one or both of newborn mannosan and cellulose ether, the cellulose ether is preferably methylcellulose, ethoxy fibre
It is more than one or both of dimension element and hydroxypropyl cellulose；
It is particularly preferred that the compound with least two proton acceptor sites is galactomannans and cellulose ether,
Preferably, on the basis of the total amount of the compound with least two proton acceptor sites, the galactomannans
Content is 10-70 weight %, is preferably 15-68 weight %, more preferably 20-65 weight %；The content of the cellulose ether is
30-90 weight %, are preferably 32-85 weight %, more preferably 35-80 weight %.
4. according to the method described in any one in claim 1-3, wherein, the hydrated alumina contains boehmite；
Preferably, the hydrated alumina is boehmite.
5. according to the method described in claim 4, wherein, it is small that the composition is placed under environment temperature and sealing condition to 72
When, the content of the gibbsite in composition after placement is higher than the content of the gibbsite in the composition before placing；
Preferably, on the basis of the total amount of the content of the gibbsite in the composition before placement, in the composition after placement
Gibbsite content at least improve 0.5%；
It is highly preferred that on the basis of the total amount of the content of the gibbsite in the composition before placement, the composition after placement
In the content of gibbsite at least improve 1%, preferably improve 1.1% to 2%.
6. according to the method described in any one in claim 1-5, wherein, the hydrated alumina is directed to hydration oxygen
Change aluminium wet gel.
7. according to the method described in any one in claim 1-6, wherein, the composition is free of peptizing agent.
8. according to the method described in any one in claim 1-7, wherein, the hydrated alumina composition use including with
The method of lower step is made：A kind of each component in feedstock composition is mixed, obtains the hydrated alumina composition, it is described
Feedstock composition contains hydrated alumina wet gel and the compound with least two proton acceptor sites, the aqua oxidation
The i values of aluminium wet gel are not less than 60%, and the dosage of the compound with least two proton acceptor sites causes finally
The composition of preparationIt is worth for less than 1.8,
The i values are measured using following methods：By 10g hydrated aluminas wet gel in 120 DEG C of 240 points of dryings in air atmosphere
Clock, w is denoted as by the quality through dry sample2, i values are calculated using Formula II,
9. according to the method described in claim 8, wherein, the i values of the hydrated alumina wet gel are not less than 61%；
Preferably, the i values of the hydrated alumina wet gel are not higher than 82%, are preferably not higher than 80%, more preferably not
Higher than 78.5%.
10. method according to claim 8 or claim 9, wherein, the hydrated alumina wet gel makes its i value be not undergo
The hydrated alumina wet gel of less than 60% dehydration.
11. according to the method described in any one in claim 8-10, wherein, the hydrated alumina wet gel is by least
After a kind of alumina hydrate gel solution alternatively carries out aging, carry out washing and separation of solid and liquid obtained from；
Preferably, the alumina hydrate gel solution is using one kind in the precipitation method, Hydrolyze method, kind point-score and rapid dehydration method
Or two or more methods are prepared.
12. according to the method for claim 11, wherein, the separation of solid and liquid carries out one or more times, at least last
Secondary separation of solid and liquid is pressure filtration and/or vacuum filter.
13. according to the method described in any one in claim 8-12, wherein, the feedstock composition is free of peptizing agent.
14. according to the method described in any one in claim 8-13, wherein, the method for the mixing for stirring and/or is pinched
Close.
15. according to the method described in any one in claim 1-14, wherein, the temperature of step (2) described drying is 60 DEG C
It is preferably 80-300 DEG C above and not higher than 350 DEG C, more preferably 110-260 DEG C.
16. according to the method described in any one in claim 1-15, wherein, in step (3), the dosage of water vapour is
0.01-0.8L/ (ming moldings), is preferably 0.02-0.6L/ (ming moldings), the molding is with aqua oxidation
Aluminium meter.
17. according to the method described in any one in claim 1-16, wherein, the method comprising the steps of (2), at least part water
Steam is the water vapour that produces during step (2) described drying.
18. according to the method described in any one in claim 1-16, wherein, the molding that step (1) obtains is sent directly into
In step (3), at least part water vapour is the water vapour that produces during step (3) described roasting.
19. according to the method for claim 18, wherein, in step (3), in roasting process, the molding will be accommodated
Container in gas draw, and using at least part gas of extraction as in the circulating air circulation feeding container；
Preferably, 10-90 volumes %, preferably 30-88 volumes %, the more preferably 60-90 volumes % in the gas of extraction is circulated
It is sent into the container.
20. according to the method described in any one in claim 1-19, wherein, the temperature roasted described in step (3) is
400-1200 DEG C, preferably 450-1100 DEG C, more preferably 500-1000 DEG C.
21. according to the method described in any one in claim 1-20, wherein, the duration roasted described in step (3)
For 1-20 it is small when, be preferably 1.5-15 it is small when, more preferably 2-12 it is small when.
22. according to the method described in any one in claim 1-21, wherein, in step (3), the container of molding will be accommodated
The heating rate that interior temperature is increased to calcination temperature is 10-400 DEG C/h, is preferably 30-350 DEG C/h, more preferably
60-300 DEG C/h.
23. according to the method described in any one in claim 1-22, wherein, it is describedBe worth for more than 1.2, be preferably 1.3 with
On, more preferably more than 1.4.
24. according to the method described in any one in claim 1-23, wherein, the hydrated alumina compositionIt is worth and is
1.2-1.8, is preferably not higher than 1.7, more preferably 1.3-1.7.
25. aluminium oxide formed body prepared by a kind of method in 1-24 as claim described in any one.
26. formed body according to claim 25, wherein, measured by mercury injection method, the aperture of the aluminium oxide formed body is in single
Peak is distributed, most probable pore size 4-60nm, is preferably 5-40nm.
27. the formed body according to claim 25 or 26, wherein, the radial direction crushing strength of the formed body is 10-40N/mm,
Preferably 15-30N/mm.
28. a kind of production forming method of hydrated alumina, this method comprise the following steps：
(1) a kind of alumina hydrate gel solution is provided, the alumina hydrate gel solution is washed, obtains the first water
Aluminium oxide wet gel is closed, the i values of the first hydrated alumina wet gel are not less than 60%, are preferably not lower than 61%, more
Preferably not higher than 82%, more preferably not higher than 80%, still more preferably for not higher than 78.5%,
The i values are measured using following methods：By 10g hydrated aluminas wet gel in 120 DEG C of 240 points of dryings in air atmosphere
Clock, w is denoted as by the quality through dry sample2, i values are calculated using Formula II,
(2) use the method in claim 1-24 described in any one by the first hydrated alumina wet gel with having extremely
Be molded after the compound mixing in few two proton acceptor sites, be optionally dry and roast, thus prepare aluminium oxide into
Type body.
29. a kind of production forming method of hydrated alumina, this method comprise the following steps：
(1) a kind of alumina hydrate gel solution is provided, the alumina hydrate gel solution is washed, obtains the first water
Close aluminium oxide wet gel；
(2) the first hydrated alumina wet gel is handled using (2-1) or (2-2), it is wet obtains the second hydrated alumina
Gel,
The first hydrated alumina wet gel and aqueous mixtures are formed slurries by (2-1), and the slurries are carried out solid-liquid point
From obtaining the second hydrated alumina wet gel；
The first hydrated alumina wet gel is carried out separation of solid and liquid by (2-2), obtains the second hydrated alumina wet gel,
In (2-1) and (2-2), the condition of the separation of solid and liquid make it that the i values of the second hydrated alumina wet gel are not low
It is further excellent more preferably not higher than 80% in 60%, preferably not lower than 61%, more preferably not above 82%
Elect as not higher than 78.5%,
The i values are measured using following methods：By 10g hydrated aluminas wet gel in 120 DEG C of 240 points of dryings in air atmosphere
Clock, w is denoted as by the quality through dry sample2, i values are calculated using Formula II,
(3) use the method in claim 1-24 described in any one by the second hydrated alumina wet gel with having extremely
Be molded after the compound mixing in few two proton acceptor sites, be optionally dry and roast, thus prepare aluminium oxide into
Type body.
30. according to the method for claim 29, wherein, the separation of solid and liquid carries out one or more times, at least last
Secondary separation of solid and liquid is pressure filtration and/or vacuum filter.
31. the method according to claim 29 or 30, wherein, the alumina hydrate gel solution be by aging or
Without being prepared into by the method more than precipitation method, Hydrolyze method, kind one or both of point-score and rapid dehydration method for aging
Arrive.
32. aluminium oxide formed body prepared by a kind of method in 28-31 as claim described in any one.
33. formed body according to claim 32, wherein, the aperture of the aluminium oxide formed body is in Unimodal Distribution, by pressure mercury
Method measures, most probable pore size 4-60nm, is preferably 5-40nm.
34. the formed body according to claim 32 or 33, wherein, the radial direction crushing strength of the formed body is 10-40N/mm,
Preferably 15-30N/mm.
35. aluminium oxide formed body in claim 25-27 and 32-34 described in any one should as carrier or adsorbent
With.
36. application according to claim 35, wherein, the carrier is the carrier of loaded catalyst, is preferably loaded
The carrier of type hydrogenation catalyst.
37. a kind of catalyst with hydrogenation catalyst effect, which contains the of carrier and load on the carrier
Group VIII metal element and vib metals element, wherein, the carrier is any one in claim 25-27 and 32-34
The aluminium oxide formed body.
38. the catalyst according to claim 37, wherein, on the basis of the total amount of the catalyst, the carrier contains
Measure as 55-94.5 weight %, preferably 64-93 weight %；In terms of oxide, the content of the group VIII metallic element is
0.5-10 weight %, are preferably 1-6 weight %；In terms of oxide, the content of the vib metals element is 5-35 weights
% is measured, is preferably 6-30 weight %.
39. a kind of preparation method of the catalyst with hydrogenation catalyst effect, this method are included in supported on carriers group VIII
Metallic element and vib metals element, wherein, the carrier is described in any one in claim 25-27 and 32-34
Aluminium oxide formed body.
40. according to the method for claim 39, wherein, the group VIII metallic element and vib metals element exist
Load capacity on carrier make it that on the basis of the total amount of the catalyst finally prepared the content of the carrier is 55-94.5 weights
% is measured, is preferably 64-93 weight %；In terms of oxide, the content of the group VIII metallic element is 0.5-10 weight %, excellent
Elect 1-6 weight % as；In terms of oxide, the content of the vib metals element is 5-35 weight %, is preferably 6-30 weights
Measure %.
41. a kind of hydrotreating method, this method is included under hydroprocessing conditions, by hydrocarbon ils with having hydrogenation catalyst effect
Catalyst contacts, wherein, the catalyst with hydrogenation catalyst effect is urging described in any one in claim 37-38
Agent or the catalyst prepared as the method described in any one in claim 39-40.
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| CN102923744A (en) * | 2012-11-20 | 2013-02-13 | 中国海洋石油总公司 | Preparation method for aluminum oxide by direct forming method |
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| CN1644656A (en) * | 2004-12-21 | 2005-07-27 | 中国科学院山西煤炭化学研究所 | Hydrogenation catalyst, its process and use |
| CN1853785A (en) * | 2005-04-27 | 2006-11-01 | 中国石油化工股份有限公司 | Silicon and boron contained alumina carrier and production thereof |
| CN1854260A (en) * | 2005-04-27 | 2006-11-01 | 中国石油化工股份有限公司 | Heavy fractional oil hydrogenation catalyst and production thereof |
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